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In Star Wars: A Force Awakens, we see that Finn (FN-2187) abandons his position as a Stormtrooper for the First Order and joins the rebellion. He also betrays the First Order by sharing some secrets about the Starkiller Base.
Are there any similar occurrences during the pre-First Order era when a Stormtrooper betrayed the Empire?
Looking for answers across the SWU (comics, movies, TV series etc.)
In the Legends continuity, there's Davin "Look, sir! Droids!" Felth, a stormtrooper assigned to Tatooine who gets caught up in the early events of A New Hope. He has a story in Tales from the Mos Eisley Cantina that covers his growing disillusionment with the Empire, starting when he's demoted for pointing out a flaw in the AT-AT design (specifically, that the legs could be tied up with cables) and culminating around the slaughter of the Jawas and Owen and Beru Lars.
He eventually
shoots his own commanding officer during the firefight in Docking Bay 94, saving Han Solo and allowing the Millenium Falcon to escape with the rebels he had been sent to stop aboard. Claiming that his commander was hit in the crossfire, he plans to stay inside the Empire and feed information to the rebels.
The implication is that he's the reason the rebels at Hoth know how to take down AT-ATs.
(Felth's name is still used for the "Look, sir! Droids!" Stormtrooper in current canon but I don't believe he has any of his old backstory or betrayal.)
To add more to TheLethalCarrot's answer, there is the case of a Tie pilot deserting the Empire after the destruction of Alderaan.
Enrolling at the Imperial Academy together to become fighter pilots for the glorious Empire is nothing less than a dream come true for the both of them. But Thane sours on the dream when he sees firsthand the horrific tactics the Empire uses to maintain its ironclad rule.
Bitter and disillusioned, Thane joins the fledgling Rebellion—putting Ciena in an unbearable position to choose between her loyalty to the Empire and her love for the man she's known since childhood.
In legends, desertions and betrayals are a more common occurrence, such as the story of CT-5539 appearing in Darth Vader and the Cry of Shadows, ex-Clone Trooper from the previous war that entered the Imperial Army as a Stormtrooper. Working directly under Vader, he will end his career by leaving the battlefield while in deployment.
Malsuum noticed that Vader was not just killing the resistance fighters, but indiscriminately targeted unarmed civilians as well. Greatly shaken by this realization, he came to doubt the righteousness of what he was doing and whether he had been wrong to trust Vader.
In an attempt to put a stop to further bloodshed, he followed Vader into the hospital, and tried to force the enemy wounded to bow down to Lord Vader, but they stood defiantly. When Vader started executing them, Malsuum called for him to stop, and Vader paused. The clone then dropped his blaster and walked away. Wookieepedia, CT-5539
The Star Wars: Empire: Betrayal comic storyline deals with a group of Imperial Moffs planning on overthrowing the Emperor and Darth Vader. It is probably more of a mutiny than anything but sounds like it would still class as a betrayal:
Shortly before the Battle of Yavin, a group of Imperial Moffs are plotting to remove the Sith Emperor and his apprentice. Their betrayal has been a long time coming, and they have prepared a group of clone stormtroopers loyal only to them. Their first task is to remove Darth Vader from the picture and send him on a fool's errand, but he is saved by Boba Fett. The conspirators plan starts falling apart when the members betray one another. The final Moff gets all the way to the Emperor's Throne Room, but is executed by Palpatine himself, who reveals he knew of the plan the whole time and wanted to remove any threats to his power.
Han Solo is also another probably example, though a bit of a grey area. He joined the Imperial Navy and through a few hoops was sentenced to death but escaped and became an outlaw. Depending on your interpretation of events you could say he betrays the Empire, especially since he ends up joining the Rebellion.
