Photoelectrocatalysis is an attractive method for extracting soluble U(VI) owing to its green and efficient advantages. The key for high photoelectrocatalytic efficiency is to design suitable photoelectrode materials. Herein, a novel uranyl-organic framework (UOF) named HNU-81 with a fourfold interpenetrating configuration was synthesized, which can insert the photosensitizer Ru(bpy)32+ successfully due to its appropriate channel size. Compared to pure HNU-81, the composite material HNU-81@Ru(bpy)3 showed enhanced light absorption and photocurrent signal, representing a more favorable charge transfer. Reflected in the reaction of photoelectrocatalytic U(VI) reduction, HNU-81@Ru(bpy)3 photoanode exhibits a removal efficiency of 81.2 %, which is more than twice that of HNU-81.