New polymerizable difunctional liquid crystals of monomers derived from 4-hydroxybenzenethiol were synthesized, characterized, and photopolymerized by the formation of anisotropic films. These films were obtained by the irradiation of the monomers in the mesophase with UV light before they were macroscopically oriented in glasses treated on the surface with polyimide and uniaxially rubbed. The monomers showed smectic and nematic mesophases. The thin films, uniaxially oriented, were optically transparent. The orientation was verified by IR dichroism, which showed a preferential order of mesogens. (C) 2005 Wiley Periodicals, Inc.