Two novel mixed valence copper coordination polymers, [Cu(2-pac)2(CuN3)(H2O)]n (1) and [Cu(2-pac)2(CuSCN)2]n (2), have been prepared through hydrothermal synthesis and analyzed for structure determination, which exhibit two- and three-dimensional structures respectively. In complex (1), zigzag chains of [CuN3]n running parallel to the c direction are interconnected by Cu(2pac)2 to form a two-dimensional layer structure. In complex (2), the arrangement of μ-1,1,3 bridging thiocyanate ligand leads to the formation of ten-membered Cu-SCN- Cu-S-Cu-NCS rings, and each Cu atom is further linked by Cu(2-pac)2 to afford a three-dimensional configuration.