Visible-light-driven organic transformation photocatalyzed by metal-organic frameworks (MOFs) under mild conditions is considered a feasible route to conserve energy and simplify synthesis. Herein, a light-sensitized, three-dimensional uranyl-organic framework (HNU-64) with twofold interpenetration and its derivatives HNU-64-CH3 and HNU-64-Cl with functionalized ligands of -CH3 and -Cl groups were obtained. These MOFs have broad optical absorption bands and suitable band energy levels in photooxidation, which makes them exhibit high activity and selectivity for the photooxidation of benzylamine to N-benzylbenzoimide under mild conditions. This work provides an efficient and simple synthetic option for oxidative coupling of amines to directly produce imines.