This report demonstrates hybrid homeotropic alignment of liquid crystals (LCs) using a self-assembled molecular (SAM) layer. 4-(4-Hep-tylphenyl)benzoic acid forms a SAM layer through hydrogen bonding with indium-tin oxide (ITO) substrate, and the LCs were aligned vertically without a polyimide (PI) layer on one side of substrate. The proposed hybrid structure featured a more stable homeotropic alignment than the LC device (LCD) with only half of a PI layer, and showed electro-optical characteristics similar to conventional LCDs with full PI layers. The SAM layer showed stable alignment and fast response in the LC cell by a simple doping method.