"Chemistry" in television shows often refers to the romantic tug between the leads. However, it goes beyond romance.
Golden Girls, for instance, worked because the four women had chemistry--they worked well together on screen, not because they were best buddies in real life but because they had that elusive ability to build a scene together with a seeming lack of effort.
Blue Bloods has multiple examples of chemistry: Reagan & Moore, Erin & Jack, Erin and Anthony.
Season 2, when Jamie goes undercover, is one of my favorites, which is unusual, since I usually dislike mafia-type storylines (and no, I've never seen Sopranos and wouldn't even bother on a desert island).
What makes Jamie's undercover story so effective is that it focuses on the rather mundane yet dangerous ripples of Jamie's work. But it is massively helped that Jamie's "in" with the Sanfino family is Noble, played by Eric Morris.
Jamie and Noble have great "bro" chemistry. They come across as two guys who would become good friends in another life, if Noble had any moral center. Jamie's guilt over Noble--and Noble's sister--is based not on the siblings getting unfair punishments. Noble and his sister have benefited from the family business. Rather, Jamie was actual friends with Noble; he "got" Noble; he knows that Noble's lack of ethics is less wilful evil and more a kind of yuppie float-through-life cluelessness.
In another type of show, Jamie and Noble would become the FBI guy and the con artist who work together to solve crimes.
That easy chemistry helps sell a story!
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