A series of group 12 metal coordination polymers with 1,2-bis(diphenylphosphino)ethane dioxide (dppeO 2 ), {[ZnCl 2 (μ-dppeO 2 )]·CH 2 Cl 2 } n (1·CH 2 Cl 2 ), [ZnBr 2 (μ-dppeO 2 )] n (2), [CdI 2 (μ-dppeO 2 )] n (4), [(HgI 2 ) 2 (μ-dppeO 2 )] n (5), [Zn(SCN)(μ-SCN)(μ-dppeO 2 )] n (6), and [Cd(NO 3 )(μ-SCN)(μ-dppeO 2 )] n (7), have been synthesized and structurally characterized. The structures of the compounds are all based on an infinite 1D chain constructed by four-coordinate metal ions and dppeO 2 ligands adopting the trans bridging coordination fashion. In the coordination polymers 1, 2 and 4, the halide ions act as terminal ligands, leading to discrete 1D chains with alternative MX 2 and dppeO 2 repeating units. The mercury compound 5 features a unique square-wave-like inorganic chain –[Hg(1)–I–Hg(2)–I]–, and the 1D HgI 2 (μ-dppeO 2 ) chains are further linked by HgI 2 bridges to form a 3D network. In the thiocyanate-containing compounds 6 and 7, the 1D chains are linked by one (6) or two (7) bridging SCN – ions to result in 2D layered structures. Solid-state emission spectra of the coordination polymers show different variations compared to the free dppeO 2 ligand, such as enhancement (1, 2, 6 and 7), shift (3 and 4) and quenching (5) upon metal coordination.