Polymerization of sulfur containing polymer has recently attracted much attention in various fields such as battery, and optical science. Especially for polymerizing high refractive index polymer requires large amount of sulfur in the polymer network. To synthesize high sulfur content polymer (HSCP) with the stable structure, there is only inverse vulcanization method is known, which is liquid method, however, miscibility and stability issues are still existing. In this thesis, initiated chemical vapor deposition (iCVD) process were employed for the surface modification of HSCP with high refractive index. Furthermore, new HSCP polymerization system, sulfur chemical vapor depsotion (sCVD) is developed. With this new sCVD system, fabrication of colorless high refractive polymer is managed.