Hollow structure materials have been proved to be excellent photocatalysts due to their advantages in the separation of electron-hole pairs. However, the synthesis of such materials is complex, time-consuming, and poor versatility. In this study, Cu-DHTP/ZIF-67 (DHTP = 2,5-dihydroxyterephthalic acid) hollow materials containing both Co and Cu were designed and synthesized by a simple one-step etching and ligand exchange strategy. It is worth noting that the bimetallic hollow catalyst can be synthesized in the presence of both Cu(Ⅱ) and DHTP within 5 min at room temperature. The synthesized hollow bimetallic catalyst has improved photoresponse performance and electron-hole pair separation ability, which results in the best catalytic performance compared with DHTP/ZIF-67, Cu/ZIF-67, and ZIF-67 when used in the photocatalytic water splitting reaction. The hydrogen evolution yield of Cu-DHTP/ZIF-67 can reach 39.7 mmol g−1, which is 6 times than that of pure ZIF-67. This study demonstrates the promising potential of Cu-DHTP/ZIF-67 photocatalyst in the field of photocatalytic water reduction and hydrogen evolution, and provides a new idea for designing and preparing more hollow structure bimetallic photocatalysts with excellent performance.