The pretilt angles of liquid crystals (LCs) could be controlled over the range, 0(o) to 90 degrees, using LC/photocurable monomer (NOA65) mixture system through UV irradiation. The pretilt angles could be controlled using LC/NOA65 mixture in planar polyimide coated LC cell, by changing the mixture ratio ranging from 99.9/0.1 to 99.0/1.0 and UV irradiation time (10 and 20min). Planar and tilted alignment was observed in LC/NOA65 mixture of 99.9/0.1 and 99.8/0.2, respectively, after UV irradiation for 20min. Finally, homeotropic (or vertical) alignment was observed in weight ratio of over 99.7/0.3. The LC alignment behavior was well correlated with the wettability of the alignment films due to the surface morphology on the alignment layer surfaces by photopolymerization-induced phase separation. This study contributes to the latest efforts to develop new method for pretilt angle control.