Dehalogenation polycondensation of 3-(4-methoxyphenyl)-2,5-dibromothiophene with Mg and a zerovalent nickel complex as well as chemical oxidative polymerization of 3-(4-methoxyphenyl)thiophene with FeCl3 gives poly[3-(4-methoxyphenyl)thiophene-2,5-diyl] P3(4-MeOPh)Th. Treatment of soluble P3(4-MeOPh)Th with BBr3 converts the OCH3 group to an OH group and gives poly[3-(4-hydroxyphenyl)thiophene-2,5-diyl] P3(4-OHPh)Th. Oxidative polymerization of 3-[3,5-di-t-butyl-4-{(trimethylsilyl)oxy}phenyl]thiophene with FeCl3 in an aqueous medium directly affords another kind of polythiophene with a sterically hindered phenolic group, poly[3-(3,5-di-t-butyl-4-hydroxyphenyl)thiophene-2,5-diyl] P3(4-OH-3,5-tBu(2)Ph)Th. An organometallic dehalogenation polymerization using a nickel complex also affords P3(4-OH-3,5-tBu(2)Ph)Th. All the polymers described above show strong photoluminescence in a region of 500-600 nm. Oxidation of P3(4-OH-3,5-tBu(2)Ph)Th with PbO2 gives stable radical species as confirmed by IR and ESR spectroscopy. Electrochemical redox behavior of the polymers is compared with that of other polythiophenes.