In this paper, polymer-dispersed liquid crystal (PDLC) films were prepared from a blend of prepolymer, liquid crystal and BaTiO3 (BTO) nanoparticle-laden nanofibres films by a polymerisation-induced phase separation (PIPS) method. By contrasting the microstructure and electro-optical curves of various proportions of monomer types, it was demonstrated that the hole size of the polymer network had a significant influence on the electro-optical nature of the PDLC films. nanofibres films loaded with different BTO nanoparticle contents were introduced into the liquid crystal mixture specimens, and the alterations in the polymer network, electro-optical nature of these specimens were analysed using SEM images, EDS and electro-optical curves. The electro-optical nature of the nanofibres films doped with PDLCs were found to be improved and the ageing resistance was greatly enhanced. Therefore, the development of PDLC films with faster response times and better electro-optical nature of reticular nanofibres films doped with PDLCs will significantly improve the promising technological applications of PDLC-based equipment for optical windows, displays, energy storage and flexible devices.