Abstract The coupling of photocatalytic hydrogen production and selective oxidation of benzylamine is a topic of significant research interest. However, enhancing the bifunctional photocatalytic activity in this context is still a major challenge. The construction of Z‐scheme heterojunctions is an effective strategy to enhance the activity of bifunctional photocatalysts. Herein, a p‐n type direct Z‐scheme heterojunction CuS/TiO 2 is constructed using metal‐organic framework (MOF)‐derived TiO 2 as a substrate. The carrier density is measured by Mott‐Schottky under photoexcitation, which confirms that the Z‐scheme electron transfer mode of CuS/TiO 2 is driven by the diffusion effect caused by the carrier concentration difference. Benefiting from efficient charge separation and transfer, photogenerated electrons, and holes are directedly transferred to active oxidation and reduction sites. CuS/TiO 2 also exhibits excellent bifunctional photocatalytic activity without noble metal cocatalysts. Among them, the H 2 evolution activity of the CuS/TiO 2 is found to be 17.1 and 29.5 times higher than that of TiO 2 and CuS, respectively. Additionally, the yields of N‐Benzylidenebenzylamine (NBB) are 14.3 and 47.4 times higher than those of TiO 2 and CuS, respectively.