Abstract: Porphyrin-based metal organic framework compounds (Al-PMOFs) with cubic columnar crystal structure were synthesized by hydrothermal method. CdZnS nanoparticles were prepared and deposited on the surface of Al-PMOFs cubic columns by chemical coprecipitation, Al-PMOFs/CdZnS nanohybrid materials with good interfacial contact were obtained. The photocatalytic activity of the prepared Al-PMOFs/CdZnS nanohybrids were evaluated by the photooxidative coupling reaction of benzylamine. The results show that Al-PMOFs/CdZnS nanocomposites have excellent photocatalytic activity and stability for the reaction. When N,N-dimethylformamide (DMF) was the solvent at room temperature, after a 7-hour-irridiation of visible light, Benzylamine can be oxidized to form n-benzyl-1-phenylmethylimine (BPMI). The conversion rate of benzylamine can reach 97%, and the selectivity of BPMI is higher than 99%. The photocatalytic activity of Al-PMOFs/CdZnS nanohybrids is 2 times higher than that of each pure component of CdZnS or Al-PMOFs, and photoactivity of the prepared Al-PMOFs/CdZnS nanohybrids can also be extended to the photooxidative coupling of many other benzylamine derivatives. The improvement of the photoactivity of Al-PMOFs/CdZnS nanohybrid materials is mainly due to the formation of Z-scheme heterojunction between Al-PMOFs and CdZnS. After many careful characterizations and analyses, it is proved that the Z-scheme heterojunction can efficiently promote the charge transfer at the interface between Al-PMOFs and CdZnS and inhibit the recombination of the photogenerated carriers on the surface of Al-PMOFs/CdZnS nanohybrids. The probable mechanism as well as the route for the transfer of the photogenerated carriers for this photocatalytic system was proposed by free radical trapping experiment.