The hydrothermal reaction of (NH4)(6)Mo7O24.4H(2)O, CuCl2.2H(2)O, and 4,4'-bipyridine yields bipyridine-ligated coppertrimolybdate monohydrate [Cu(4,4'-bipy)(H2O)(Mo3O10)]-H2O in the monoclinic system with space group of C-2/c and cell parameters of a = 15.335(2) Angstrom, b = 15.535(2) Angstrom, c = 15.106(2) Angstrom, beta = 101. 162(2)degrees, V = 3530.7(9) Angstrom(3), and Z = 8. Its structure consists of one-dimensional infinite [Mo3O10](2-)}(infinity) chains linked through {Cu-2(H2O)(2)(4,4'bipy)} units. The Mo-O chain contains distorted {MoO6} octahedra connected through corner-sharing oxygen atoms into infinite chains along the c direction and each chain is, located in the channel formed by four adjacent crossing chains of {Cu(4,4'-bipy)(H2O)}(n)(2n+). The crystal shows weak conductivity through Mo-O chain along the c direction and insulating property along either a or b direction. Furthermore, a crystalline bimetallic oxide, CuMo3O10, forms when the title compound undergoes thermal treatment in N-2 atmosphere after the complete removal of the ligands.