The developed methodology describes an environmentally benign protocol for electro-oxidative CF₃-radical generation, followed by cascade cyclization fabricating an isoxazoline scaffold from a β,γ-unsaturated oxime. Consecutive C–O and C–C bond formations were achieved through this method featuring mild, robust, and scalable reaction conditions and broad substrate scope. Mechanistic studies revealed the necessity of anodic oxidation for the cascade process. Further conversion of the isoxazoline afforded other valuable derivatives.