Lewis- and Brønsted-acid catalyzed 1,3-dipolar cycloaddition between azomethine ylides and unsaturated compounds is an important strategy to construct five-membered N-heterocycles. However, such a catalytic route usually demands substrates with an electron-withdrawing group (EWG) to facilitate the reactivity. Herein, we report a TiO2 photocatalysis strategy that can conveniently prepare five-membered N-heterocyclic imidazolidines from a common imine (N-benzylidenebenzylamine) and alcohols along the route of 1,3-dipolaron azomethine ylide but without pre-installed EWG substituents on the substrates. Our EPR results uncovered the previously unknown mutual interdependence between an azomethine ylide and TiO2 photo-induced hvb+/ecb- pair. This transformation exhibited a broad scope with 21 successful examples and could be scaled up to the gram level.