There are male characters on TV that are nice, and then there are guys that consider themselves nice and feel like because of that they are entitled to something, usually women.
You know the type, he believes in the friend zone because he thinks multiple women in his life put her there even though he is a "nice guy." That quickly turns into the guy believing that women owe him something because he isn't like all those other guys, which means he deserves any women he wants.
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At the end of the day, Nice Guy Syndrome can be associated with some of the worst guys and characters, mostly because they hide behind a facade and use that to manipulate others by trying to make them feel bad for him.
TV characters that embody that are usually main characters with relationships that leave more to be desired. Here is a slideshow of a few examples of just that.
Michael Scott - The Office
Michael was a character that was lonely above all else, but the way he treated women left a lot to be desired. More than that though, he consistently saw himself as someone who deserved the kindness that he didn't always give off himself, especially to women.
Ted Mosby - How I Met Your Mother
Ted Mosby could be the poster boy for Nice Guy Syndrome, his entire journey on How I Met Your Mother was him wallowing about the fact that he deserves to be with someone who doesn't want to be with him. His treatment of Robin and her feelings is nonexistent, no matter how much she moves on or points out that what they want for one another doesn't align. This is all hidden behind a story about how he meets the mother of his children, except that, is all she seems to be. He has no respect for this person he chose to spend his life with, only relating it back to how now he wants to once again be with someone that he never got over. The true issue though is the way that the show not only rewards but promotes this mentality, all the way to the end.
Finn Collins - The 100
Knowing you still have a girlfriend and expecting the girl you decided to cheat with to just understand? Finn definitely relied on his "nice guy" appeal to excuse examples of him being a really inconsiderate person. He heavily enjoyed comparing himself to Bellamy because of that, considering himself somehow superior when he was far from that.
Winn Schott - Supergirl
There was just something about the way Winn felt like he and Kara belonged together that exuded all the wrong energy. If there was anyone who could have believed in the friend zone, Winn in the first season of Supergirl did.
Walter White - Breaking Bad
Walter White is interesting because it is very possible that the entirety of the show comes from the fact that he suffers from Nice Guy Syndrome.
Ross Geller - Friends
The best example has to be from the show that invented the term friend zone, a concept that doesn't even exist. Ross was fixated on the notion that he belongs with Rachel, but when they actually got together he was far from a good person. He used the idea of him being a nice guy to excuse his obsessive jealousy and inability to root for his girlfriend prospering in a way that didn't include him. This was really only the beginning, with Ross never outgrowing this pattern for seasons to follow.