We synthesized a novel Cu8 cluster and employed it as a building block to further obtain a copper cluster-based MOF material (CCMOF). Compared with the Cu8 cluster precursor, the periodically constructed CCMOF exhibited better structural stability, and showed enhanced photocatalytic H2 evolution performance due to efficient mass/charge transportation benefitting from the ordered porous framework structure. This two-step grafting construction strategy is of great significance to the exploration of copper clusters in catalytic applications.