The pretilt angle of liquid crystal (LC) molecules in LC cells was manipulated by adding a mixture of two photocurable monomers, alkyl acrylate and biphenyl diacrylate, into the LCs after the UV treatment. The hexyl acrylate and octadecyl acrylate were applied to examine the alkyl chain length effect on the pretilt angle control under the condition of a fixed concentration of biphenyl diacrylate. The LC alignment was continuously adjusted from homogeneous to homeotropic alignment in the polymer-stabilized LC system by simply increasing the alkyl acrylate concentration in the LCs. At a given molar concentration of alkyl acrylate, the addition of octadecyl acrylate exhibits higher pretilt angle than that of hexyl acrylate. Both the pretilt angle of the LCs and advancing contact angle of water on the inner surfaces of LC cells simultaneously changed due to surface chemical nature and surface roughness. The pretilt angle increases along with an increase in the advancing contact angle. As a consequence, the surface advancing contact angle acts as an index for pretilt angle control.