Thermal polymerization of bis[4-(4-bromophenylthio)phenyl] disulfide (I), bis[4-(4-bromophenyloxy)phenyl] disulfide (II) and bis[(4-(4-bromophenylsulfony)phenyloxy)phenyl] disulfide (III) was carried out at 250 degrees C in diphenyl ether. The resulting poly(thioarylene)s show high crystallinity and high thermal stability. The blends and copolymers of poly(thioarylene) were also prepared, whose thermal properties were investigated by DSC measurements.