A novel approach of [3+3]‐cycloaddition of N,N′‐cyclic azomethine imines with γ‐hydroxy‐α,β‐unsaturated carbonyls was developed. Bicyclic oxadiazines were readily obtained in moderate to good yields from the reactions of various γ‐hydroxy‐α,β‐unsaturated ketones, including aromatic and aliphatic ketones, with N,N′‐cyclic azomethine imines under mild conditions, demonstrating the broad substrate scope.