The photocatalytic co-reduction of CO2 and NO3− is a sustainable method for urea synthesis under mild condition. However, the low photocatalytic yield of urea is a challenge, due to the sluggish kinetics of the C–N coupling reaction. Herein, we successfully designed a TiO2 nanoparticle modified Cu nanorod photocatalyst (TiO2@Cu) for simultaneously promoting the NO3− reduction and CO2 reduction reaction in the photocatalytic synthesis of urea.