We synthesized a series of vitamin-based and biocompatible tocopherolsubstituted polystyrene (PTOC#, # = 20, 40, 60, 80, and 100), where # is molar ratio of tocopherol moiety, using polymer analogous reactions to investigate their liquid crystal (LC) orientation properties. LC cell fabricated with polymer film having higher molar ratio of tocopherol side group showed vertical LC orientation behavior. The vertical orientation behavior had a strong relation with surface energy value of films made of PTOC# series polymer. Vertical orientation was generated by nonpolar tocopherol moiety having long and bulky carbon groups. Good electro-optical characteristics, e.g. voltage holding ratio and residual DC voltage, and LC thermal and UV stabilities were observed for LC cells fabricated with PTOC100 as a LC orientation layer. Therefore, it was first found that the eco-friendly tocopherolbased materials can produce a green vertical LC orientation system.