The reaction of diphenyldipyridinogermole with [Cu2I2-(PPh3)(3)] in THE afforded a complex with high thermal stability. Crystals with linear polymeric structures (determined by single crystal X-ray diffraction study) emitted orange phosphorescence with the quantum yield of 25%. The sufficient solubility of the complex permitted the fabrication of a complex-doped poly(methyl methacrylate) (PMMA) self-standing phosphorescent film.