A series of novel metal complexes, [Cu2(dppm)2(OOCL)]2[NO3]2 (1), [Ag2(dppm)2(OOCL)2] (2) and [Au2(dppm)2(OOCL)2] (3) (dppm = bis(diphenylphosphino)methane, L = 2-cyano-3-(4-(diphenylamino) phenyl)acrylic acid) were prepared and structurally characterized by X-ray crystallography. Their optical properties were investigated by absorption and fluorescence spectra. The fluorescence spectra of the complexes showed red shifts relative to that of L, which exhibited the same tendency as the absorption spectra. In addition, the ability of 1–3 to generate electrochemiluminescence (ECL) were assessed in acetonitrile solutions, they exhibited a highly enhanced stable ECL emission compared to the free ligand (L). Especially, the ECL intensity of 1 was approximately 30 times greater than that of L.1–3 exhibited a highly enhanced stable ECL emission compared to L. Especially, the ECL intensity of 1 is approximately 30 times greater than that of L. This implies that the introduction of heavy metals strengthens the spin–orbit coupling effect, improves the luminous efficiency of the materials and then enhances the ECL emission.