The asymmetric oxidation of poly(phenylvinyl sulfide) (poly-Ph VS) and poly(t-butylvinyl sulfide) (poly-t-BuVS) was carried out with optically active percamphoric acid, and the optically active polysulfoxides were obtained. The values of the specific rotation for the oxidation products of poly-PhVS and poly-t-BuVS were + 1.0 (having 56% of sulfoxide unit contents) and +9.1 (49%), respectively. The specific rotation of the product increased with increasing the contents of sulfoxide units. The optical rotatory dispersion curves of the oxidation products of poly-PhVS and poly-t-BuVS were positive curves and were found to fit the simple Drude equation. The λc values of the oxidation products (poly-PhVS, 271 mμ; poly-t-BuVS, 212 mμ) suggested that the chromophore which caused optically activity was the sulfoxide group. Similarly, the asymmetric oxidation of t-BuVS–MMA copolymer, t-BuVS–styrene copolymer, and PhVS–MMA copolymer was carried out, and the optically active copolysulfoxides were obtained. Furthermore, the biosynthetic oxidation of poly-PhVS and PhVS–maleic anhydride copolymer treated with aqueous KOH was carried out using Aspergillus niger or Penicillium notatum in Czapeck solution, and the optically active polymers were obtained.