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Before Season 1
In "Ladybug & Cat Noir (Origins - Part 1)", Nino was forced to move to the front row of the classroom by Miss Bustier. He ignored Chloé when she sat behind him and fought with Marinette. He went to Parc des Princes for PE with Mr. D'Argencourt. He was not seen from again after Stoneheart attacked Lê Chiến Kim.
In "Stoneheart (Origins - Part 2)", Nino didn't greet Adrien when he first entered the classroom because he thought he was rude like Chloé. After he saw Adrien try to get the gum off Marinette's seat, Nino introduced himself and decided Adrien needed better friends. When Stoneheart reappeared, he was the first person to run. The next day, he greeted Adrien and encouraged him to talk to Marinette.
In "the Bubbler", Nino was upset that Adrien wasn't allowed to have a birthday party. He decided that he should visit Mr. Agreste and try to change his mind. Nino managed to change Gabriel's mind, but not in the way he wanted; instead of succeeding in getting Adrien permission to throw a birthday party, he succeeded in being banned from being Adrien's friend. Upset, Nino went to the park to try to calm down, but he only became more angry when he saw parents not letting their kids have fun. Hawk Moth sensed Nino's frustration and anger and akumatized him into the supervillain, Bubbler. The first thing Bubbler did was bubble all the adults and sent them into space. The second thing he did was throw Adrien a birthday party. When Ladybug and Cat Noir interrupted the party, he bubbled them, but they came back. The second time, he bubbled the other kids at the party and then chased after the heroes. Ladybug and Cat Noir caught Bubbler, captured his akuma, and returned the city to normal. The next day, he and Adrien walked into school together, their friendship solidified.
In "Mr. Pigeon", Nino sat by Adrien in class and supported him when the derby hat competition was announced and during the competition itself.
In "Timebreaker", Nino cheered on Alix and Kim. He helped Marinette hold the banner she made, but because he was cheering so enthusiastically, he ended up making her drop Alix's watch. Timebreaker made him disappear in both timelines, but Ladybug brought him back with Miraculous Ladybug.
In "Lady Wifi", Alya dragged Nino out of the school to tell him her theory about Ladybug's identity. They bonded over their best friends being missing and then Alya told Nino she thought Ladybug was Chloé. Nino did not believe her. Alya roped him into helping her prove that Chloé was Ladybug. Nino had to distract Chloé while Alya took a picture of Chloé's locker. He was successful in distracting her, but Alya was caught anyways. When Marinette arrived, he told her about Alya's theory and that Alya was suspended for a week. He ran home, worried, after Lady Wifi attacked the school.
In "the Evillustrator", Nino was paired up with Adrien and Alya for their particle physics presentation.