Irina Pouffanovitch, dubbed "The Seductive Witch," antagonizes villagers and Class 3-E students within a fantasy RPG setting. She wields enchantment and seduction, exploiting her appearance to manipulate targets into compelled obedience. Her base, the Tower of Temptation, serves as a prison for captured villagers and a lure for Class 3-E. When her disguise as an elderly woman tricks students like Hiroto Maehara and Taiga Okajima into offering aid, they fall under her spell. She traps the female students and attempts to eliminate the unaffected Nagisa Shiota and Karma Akabane by ordering their expulsion.

Her enchantments fail against Koro-sensei due to his concealed immunity as the Demon King, part of his counterstrategy. While she focuses on him, Commander Karasuma frees the captured students. Koro-sensei rescues Nagisa and Karma, revealing his feigned enchantment and enabling the escape and liberation of the villagers. Defeated, Irina surrenders and ceases her antagonistic actions.

She later joins Class 3-E as an instructor. In this role, she educates students on recognizing and resisting enchantments and manipulative tactics, leveraging her firsthand expertise to prepare them for mental resilience challenges.