Aang and Mai did not interact that much at first but the two were natural enemies, being on different sides of the war. Aang was the avatar who was supposed to end the war and bring peace to the world while Mai was in a group along with Azula and Ty Lee with the goal of capturing Aang. However, they never faced each other one-on-one. Mai usually faced the other members of Team Avatar instead. Mai eventually betrayed Azula and the Fire Nation, and while it was only for Zuko, she and Aang were no longer enemies. They were both at the Jasmine Dragon in Ba Sing Se after the end of the war.
Despite the fact that it is a crack pairing, Maiaang has a decent amount of popularity in the Avatar fandom. It is commonly shipped along with Zutara because it solves the issue of Aang and Mai having love interests without interfering with any other ships. Some also see Maiaang as an "opposites attract" ship due to the fact that Aang is cheery and playful while Mai is cold and reserved. Maiaang most commonly rivals the Kataang and Maiko ships.