Polyoxometalate-based copper clusters as promising hydrogen evolution catalysts are rarely reported. Here, [Cu5(OH)4(H2O)2(A-α-SiW9O33)2]10- (1) was tested as an effective molecular catalyst for visible-light-driven H2 evolution. A high turnover number (TON) of 718.9 was achieved in the photocatalytic reaction. Many stability experiments showed that compound 1 could maintain its structure intact during the photocatalytic process.