7,8‐Dimethoxy‐3‐methylalloxazine was immobilized on mesoporoussilica (MCM‐41) to provide a heterogenized flavin photocatalyst. Thus, the prepared heterogeneous catalyst 2 was found to sensitize the visiblelight [2+2] cycloaddition of various types of dienes to produce corresponding cyclobutanes in high yields and diastereoselectivities. Use of 2 enables procedures which are advantageous owing to