Vertical alignment of liquid crystals (LCs) was implemented by forming an in situ self-assembled molecular layer on hydrophilic indium tin oxide (ITO) electrodes. Improvement in hydrophilicity of the ITO electrode according to ultraviolet (UV) irradiation time was confirmed. The self-assembled molecular layer offered stable vertical alignment of nematic LCs via hydrogen bonding between 4 '-heptylbiphenyl-4-carboxylic acid and the hydroxyl groups on the ITO surface. Further, the electro-optical property of the LC cell irradiated by UV light was investigated to confirm the improved performance of the LC device.