This paper introduces homogeneous liquid crystal (LC) orientations on chemically modulated polystyrene (PS) surfaces using various ion beam (IB) exposure times. Transparent PS was replaced with conventional polyimide material. As a non-contact process, the IB bombardment process induced LC orientation parallel to the IB process. Through x-ray photoelectron spectroscopy, it was shown that the chemical compositional changes of the IB-irradiated PS surfaces were determined as a function of IB exposure time. Using this analysis, the optimal IB bombardment condition was determined at an IB exposure time of up to 15 seconds. Moreover, thermal stability on IB-irradiated PS surfaces were carried out which showed that a relatively high IB exposure time induced a thermally stable LC alignment property.