Abstract: The title compound has been synthesized by the reaction of (NH_4)_2WS_4 and CuCl_2·2H_2O in pyridine solution, 4[CuCl(C_5H_5N)_4] ·[W_(10)O_(32)]·2(C_5H_5N)·3H_2O is triclinic, space group P1, a=1.3555(7), b=1.3666(5), c=1.7860(13) nm, α=69.08(4)°, β=87.39(5)°, γ=70.72(4)°. V=2.907(3) nm, z=1. D_m=2.56 gcm~(-3). The structure was solved by Patterson method and Fourier methods. The final R is 0.046. The result indicates that the crystal is composed of W_(10)O_(32)~(4-), [CuCl(C_5H_5N)_4]~+, C_5H_5N and H_2O. The structure of W_(10)O_(32)~(4-) is shown in Fig.1. The W atom is coordinated by six O atoms of octahedra, which united by edges and corner. The structure of [CuCl(C_5H_5N)_4]~+ isshown in Fig.2. The Cu atom is coordinated by one Cl and four N atoms that form slightly deformed pyramid. This kind of [CuCl(C_5H_5N)_4]~+ cation has not been reported before. C_5H_5N and H_2O molecules are distributed in the interstices of the packing of the ions.