A new microporous luminescent coordination polymer [(CH3)(2)NH2] center dot [Cu-2(CN)(3)] (1) with channels occupied by dimethylamine cations was synthesized due to the inducing effect of 2-(2'-pyridyl)imidazole. Complex 1 exhibits bright-green emission in the solid state, and its emission intensity would be significantly enhanced, especially by DMAc and cupric ion after immersing the as-synthesized crystals of 1 into common organic solvents or methanol solutions of various metal ions. In addition, 1 exhibits photo catalytic activity for the degradation of RhB and MB under natural light and is stable during the photocatalysis process. Thus, 1 can act as a multifunctional material for selectively sensing of Cu2+ and effectively photocatalytic degradation of dyes.