Developing efficient photocatalysts for direct oxidative coupling of alkenes and amines with O-2 under mild conditions is very significant. Herein, ZnW-PYI is well-designed by assembling a [PZnW11,O-39(H2O)] (5-) photooxidation catalyst and chiral aminocatalyst pyrrolidine-2-ylimidazole (PYI) via a coordination model. ZnW-PYI efficiently catalyzed the synthesis of imines from alkenes and amines using O-2 as the oxidant through nucleophilic catalysis by employing pyrrolidine as an organocatalyst. Combining a polyox-ometalate and PYI within one single framework is an effective approach not only for stabilization and heterogenization of the redox-active catalyst and aminocatalyst but also for realization of compatibility between the reaction intermediates and synergy of multiple catalytic cycles.