Polyoxometalates (POMs) are known for their photocatalytic hydrogen production activity, but their solubility and limited stability often restrict their practical applications. Herein, we designed and solvothermally synthesized two new Cu-H2bpz (3,3',5,5'-tetramethyl-4,4'-bipyrazole, abbreviated as H2bpz) compounds, namely, Cu0.5(H2bpz)(NO3) (1) and Cu(Hbpz)(Cl)·DMF (2), and three new polyoxometalate-based Cu(II)-pyrazolate compounds, namely, Cu(PW12O40)0.5(H2bpz)2(H2O)·(OH)0.5(H2O)5.5 (3), Cu(HPMo12O40)(H2bpz)2(H2O)2·(H2O)4 (4), and Cu2(SiW12O40)(H2bpz)3(H2O)3·(H2O)6 (5). Compound 3 (Cu(PW12O40)0.5(H2bpz)2(H2O)·(OH)0.5(H2O)5.5) exhibits the best photocatalytic activity of 44.4 μ L h-1 g-1, which may be related to the stability of compounds. Herein, the solvothermal method has been proven to be an effective method in synthesizing stable organic-inorganic hybrid compounds with soluble POMs, metal ions, and organic ligands. Thus, heterogeneous catalysts with outstanding solar-light-driven photocatalytic properties were obtained.