A series of novel metal complexes were synthesized containing an Ir-cyclometalated bichromophore as a visible-light sensitizer. A new bichromophoric unit containing a naphthyl substituent and methyl substituents on the 2-phenylpyridine chelating ligand was synthesized and characterized for the first time. According to the increased crystallinity of the bichromophoric unit, novel Ir–M metal complexes (M = Pd, Mn, and Ir) were synthesized and fully characterized. The novel Ir–Pd complex maintained photocatalytic activity toward styrenes under visible-light irradiation, and polymerization with p-chlorostyrene, copolymerization with styrene and p-chlorostyrene furnished corresponding polymers.