A vertically-aligned liquid crystal (LC) device with fast-switching LC molecules and excellent electro-optical properties is proposed. The proposed method employs a mixture of a polyimide to achieve the desired vertical alignment, and a mesogenic photocrosslinker to obtain the fast LC response. More specifically, the photocrosslinkers were photopolymerized by UV irradiation under an electric field to pre-tilt the LC molecules. In addition, upon increasing the number of functional groups in the photocrosslinker, faster switching properties were exhibited due to enhanced pre-tilting. Following UV irradiation, the proposed system also exhibited stable homeotropic alignment properties similar to those of conventional polyimides.