A newly synthesized Hofmann-type bimetallic coordination polymer, [Cd(II)(3-methylpyridine)2][Au(CN)2]2, was luminescent with emission peaks at 400 nm, 440 nm, 490 nm and 550 nm (shoulder) under irradiation at 360 nm, whose multiple peak character in the emission spectrum was rationalized in terms of the vibrational structures in the interactions between the Au atoms in adjacent layers.