I don't know what you're expecting of me
Your sister...she hates me, and I don't know why!
Okay, let's get this over with up front:
I'm
I understand why it's not canon, and I can certainly understand why the creators felt the need to mock it at the San Diego ComiCon in 2008 (and the outcome was delightfully hilarious, I admit). I even feel a bit guilty about liking this ship myself, since you basically have to have no soul if you're okay with anything that makes Aang cry (and Zuko x Katara—or anyone besides Aang x Katara—would definitely make Aang cry).
But here's the thing. Zuko's a screwed up kid who needs someone who would listen to him without judgment…and also be willing to kick his ass. Katara has a solid sense of family and justice, but has led a sheltered life that makes it easy for her to hate those who've done wrong without having to look at all sides of an issue. Unlike canon pairings of Aang and Katara or Zuko and Mai, Zuko and Katara's personalities both challenge and balance each other out (opposing yin/yang elements, anyone?). They force each other to grow into better people and to take responsibility for their own actions. And to me, that makes for a much more interesting, not to mention healthy, relationship than the ones we actually get in canon.
Leaving aside the romantic element, Zuko and Katara do have an interesting, multifaceted relationship—though I wish they'd had more time to interact throughout the series. In season one, Zuko is essentially That Jerk Who Holds Katara's Necklace Hostage (S01E09, "The Waterbending Scroll") and That Jerk Who Threatens Aang And Therefore Must Get His Butt Kicked (S01E19-20, "The Siege of the North"). Their only interactions are a few fights, which Katara mostly wins. Katara seems aware of Zuko as a threat Team Avatar needs to keep an eye on, but other than that, he's not much on her mind. Zuko, for his part, is pretty condescending toward Katara and sees her as little more than a means to get to Aang.
But by season two, we're starting to get hints of how their relationship is changing. When Azula injures Iroh during a showdown, Katara offers to help—and certainly would have if Zuko hadn't freaked out and told her and the others to get lost (S02E08, "The Chase"). Despite everything Zuko's done, Katara obviously realizes Iroh is important to him, and it's in her nature to help anyone she can.
Their key scene in season two is when Zuko admits to Katara that his mother was taken from him because of the war, just like Katara's mother was from her (S02E20, "The Crossroads of Destiny"). Katara seems to really consider for the first time that there might be reasons behind Zuko being a total mess, and that makes her pity him and feel a bit guilty for yelling at him. Zuko, for his part, realizes that the things he's done have had real consequences for other people. It ain't a declaration of love, and it's not even really friendship at this point, but they do get a bit closer to understanding each other.
And then Zuko totally screws it up by siding with Azula so he can return to the Fire Nation.
You'd think Aang would be most at odds with Zuko, given how long Zuko's been after him, but it's really Katara who is most angry with Zuko, taking the longest time of any of Team Avatar to accept he's finally changed. This is probably because, as with all of her relationships, Katara is emotionally invested in her relationship (such as it is) with Zuko. To her, he's the face of the enemy throughout much of first and second season. When they are briefly imprisoned together in Ba Sing Se, Katara begins to feel pity and sadness for just how royally screwed up Zuko is. And when he chooses Azula's side instead of Aang's, Katara feels personally betrayed. Katara wants to believe the best of people, so she has a hard time understanding someone so morally confused as Zuko.
Ultimately, however, she's able to forgive him, which in turn allows him to forgive himself. This comes about when Zuko helps Katara find the man who killed her mother (S03E16, "The Southern Raiders"). Zuko means well by this, but in some ways he's really just promoting her baser instincts. Aang warns them that this is about revenge, but Zuko argues it's about closure. They're both right. Some of this is about Zuko wanting to get Katara to stop hating him—long after the rest of the group has more or less accepted Zuko, Katara is still hurt, having been the first to trust him back in Ba Sing Se. Zuko seems to think helping Katara find her mother's killer will help her deal with her anger in a more productive way than lashing out at him. So instead of piling on moral judgment about whether or not she should kill the man who ruined her family, he follows her quietly and lets her do what she feels needs doing.
Whatever their past issues, Zuko obviously cares about Katara, not only because she's scary and can kick his ass, but because she becomes a calm center of moral and emotional support for him. When Zuko finally has the opportunity to apologize to Iroh, he worries that Iroh will hate him; but Katara tells him Iroh will forgive him and helps Zuko summon up the courage to face his uncle--in what is, quite possibly, one of the best scenes in the entire series (S03E19, "Sozin's Comet, Part 2: The Old Masters").
Katara is the one Zuko asks to be with him when faces Azula, and when you get down to it, Katara's the one who actually takes Azula out. But before that she's supportive enough to let Zuko fight Azula alone in an agni kai (though she warns him that Azula's just trying to separate them, since she can't take them both). Zuko holds out pretty well on his own (for once), but when Azula tries to use lightning on Katara, Zuko immediately puts himself in harm's way to protect her. Obviously, Katara's become extremely important to him, and if her relief that he survives is any indication, she's decided he's worth being concerned about, too.
Even if you're not a rabid Zutara fan (
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