Abstract The construction of heterostructure composites is an efficient way to widen the spectral response range and reduce the photogenerated electrons-holes recombination, but it is still a challenge to realize the maximizing the photocatalytic performance of different photoresponsive material, especially at low temperature. In this work, we construct a series of ZnO@gCN-UA/MA composites by first designing a series of UA@ZIF-8@MA sandwich templates and then calcining these sandwich templates at high temperature. During the pyrolysis process, ZIF-8 and melamine precursors would convert into ZnO and gCN structure so as to form the ZnO@gCN composite at high temperature, while urea molecular would decompose to release ammonia molecules which rush out from the interior of ZIF-8 to make the ZnO@gCN-UA/MA composites become fluffy and porous. Detailed characterization results reveal that the ZnO@gCN-UA/MA composites exhibit enhanced spectral response range and the lower charge-carrier recombination rates. When being used in photocatalytic oxidative coupling of amines at low temperature under air condition, the optimal ZnO(0.1)@gCN-UA/MA catalyst exhibits excellent activity, affording the imine product with 96% yield. Moreover, the catalysts also exhibit a wide substrate compatibility and recyclability.