In this study, we applied the non-contact photo-polymerisation method in fabricating pseudo-polyimide (PI) liquid crystal (LC) devices with vertical alignment copolymer films, in the hope of solving the problems associated with traditional rubbing alignment processes. We mixed different photo-polymerisation-type acrylic monomers and negative dielectric anisotropy LC at proper weight percentages, and induced phase separation behaviour between the photo-polymerisation-type acrylic monomers and the LC molecules in the LC mixture solution through ultraviolet light irradiation, thereby forming copolymer films with vertical alignment effects. We further conducted preliminary characterisation of the alignment mechanism, photo-polymerisation, etc., of the LC molecules and investigated their interactions with alkyl acrylic monomers with different carbon chain lengths (the analogue of alkyl side chains in traditionally used vertical alignment-type PI) and electro-optical properties such as the transmittance, contrast ratio, and response time.