✓ Dean Winchester (Supernatural)
Dean's the lone wolf of the team, often going out on his own, taking cases without telling Steve, getting into trouble. And then calling in for back-up at the last minute. He's the loose canon with the dark backstory, but has survived more than one apocalypse so is also something of a legend and would be treated with respect by his teammates - provided he's not snarking it up with Steve or Caroline, that is. When not saving people and hunting things, he's the muscle of the team and steps up to do the dirty work when no one else will.
✓ Joan Watson (Elementary)
Consulting detective and still going through her training (with one Sherlock Holmes, who couldn't be bothered to be part be part of a team), Joan is one of the more level-headed members and is skilled in deductive reasoning. With her background as a surgeon, she sometimes doubles up as the team medic but definitely wouldn't do it if they had any other option. I imagine that with her people skills, she, Caroline, and Dean often end up getting the undercover missions. She also gets along swimmingly with Ichabod, whom she usually researches and consults with regarding their more mythologically specific cases.
✓ Auggie Anderson (Covert Affairs)
With his tech skills and sometimes surprising abilities in hand-to-hand combat, Auggie is the watchtower of the team, monitoring missions from a distance and providing back-up when needed. Since Steve, who takes command, prefers being on the ground, Auggie serves as his eyes and ears and will often be found directing him via communicator through more difficult cases. He also spars with Joan and Caroline in his free time, and enjoys bribing Dean with new and improved weapons.
✓ Steve McGarrett (Hawaii Five-0)
Steve is the leader of the group with his gung-ho, shoot-first-ask-questions-later persona. He prefers being present during missions and knows what it's like to move around in gray areas to get a job done. Because he's as stubborn as Dean, the two will often butt heads and be on the outs - but can, likewise, count on each other when the need arises. (In particularly difficult situations, however, they can count on Joan and a phone call from either Sam or Danny to set them straight.)
✓ Caroline Forbes (The Vampire Diaries)
Although Dean is a seasoned hunter, Caroline is an actual vampire. And it pays to have someone with a specific skill set like that. Zooming in and out of crime scenes and acting as the unexpected muscle of the team, Caroline relies greatly on her vampiric abilities (super strength, speed, healing, heightened senses) to get the job done. She is often also sent out on undercover missions because of her disarming personality. She gets along quite well with everyone except Dean, as the two are usually found arguing about one thing or other.
✓ Ichabod Crane (Sleepy Hollow)
Ichabod takes the lead on research with his eidetic memory and knowledge of the occult. He is also fluent in a number of languages which include Modern and Middle English, German, and Greek. Like Joan, he has a keen sense of observation and can be counted on to spot things the others don't. He, Auggie, and Joan often work together when scoping out a crime scene while leaving the heavy lifting to Steve, Dean, and Caroline. However, when placed in immediate danger, Ichabod is also an experienced marksman and can hold his own in hand-to-hand combat. In his spare time, he enjoys tinkering around with Auggie and learning more about the modern world.
✓ Adalind Schade (Grimm)
Resident witch (or Hexenbiest, if you want to get specific), Adalind is poised, seductive, and utterly ruthless when it comes to power; this is something she has in common with Cora, which is why they are often found working together and wreaking havoc. She's the sort of girl who would sell her unborn baby to regain her abilities and sleep with unsuspecting Royals to create an upset in their line of succession.
✓ Mei Chen (Intelligence)
Mei Chen is a human who was implanted with a special chip in her brain, which allows her control over technology and the ability to render crime scenes and data as if they were memories. She is able to enter programming and steal or rework classified information to her advantage, and makes the perfect partner for Moriarty. Well, maybe not partner per se. But they do make a frightening enough pair.
✓ Jim Moriarty (Sherlock)
Consulting criminal extraordinaire, Moriarty pools all the baddies together and yanks the right strings to make them do what he wants without them knowing it. He is manipulative, arrogant, a complete sociopath, and can get quite obsessive given the right nemesis. I imagine him thriving as the Big Bad and throwing out all these 'minor' cases at the dream team, until they realize he's been behind everything all along. In his spare time, he enjoys a cup of tea with Hannibal and frequents Baker Street.
✓ Hannibal Lecter (Hannibal)
Silently intimidating, dignified, cold, and calculating, Hannibal is frighteningly observant and has the uncanny ability to get into a person's mind, plucking and pulling until he's unraveled all their dark secrets and used them to amuse himself. He's a psychiatrist who works with the FBI and doubles up as a serial killer known as the Chesapeake Ripper, of course, without their knowledge. He sees his victims as pigs and is known to consume them after he kills and mutilates them. Like Moriarty, he can get terribly obsessive as well when faced with a promising nemesis.
✓ Melisandre (Game of Thrones)
A mysterious priestess who prefers working from the sidelines, Melisandre often takes on jobs alone and trusts completely in her own abilities. She is granted visions through fire, scoffs at non-believers, and is able to control dark shadow creatures to do her bidding. Although no one knows her true intentions, she does appear to side with whomever her god chooses, whether or not the person is actually evil.
✓ Cora (Once Upon A Time)
Previously a simple miller's daughter with an intense hunger for power, Cora eventually worked her way up the ladder by partnering with Rumpelstilskin, known as the Dark One. As he taught her to use dark magic, she continued to hone her craft until she herself became a formidable foe and allowed her desire for greatness to consume her. Her abilities include a knowledge of various potions, a collection of evil spells, and the ability to shapeshift to confuse her enemies.