A study was conducted to demonstrate that intramolecular donor-acceptor (D-A) regioregular Poly(hexylphenanthrenyl-imidazole thiophene) (PHPIT) exhibited enhanced hole mobility for heterojunction solar cell applications. It also demonstrated the synthesis of the thiophene-type homopolymer presenting phenanthrenylimidazole moieties. The synthetic approach involved the polymerization of the planar phenanthrenyl-imidazole moiety-tethered thiophene monomer. It was assumed that the presence of the hexylphenanthrenyl-imidazole moieties conjugated to the thiophene units was to reduce the band-gap of the polythiophene and that the hexyl substituents improved the solubility of the polymer. The 2-(2,5-dibromothiophen-3-yl)-6,9-dihexyl-1-(4-hexylphenyl)-1H- 1Hphenanthro-[9,10-d]-imidazole (HPIT) monomer was polymerized using a Grignard metathesis approach. The presence of the bulky hexylphenanthrenyl-imidazole unit led to high selectivity during the reaction, resulting in highly regioregular (PHPIT).