Aggregation-induced emission (AIE) polymers have attracted increasing attention due to good processability, film-forming ability, and ease of functionalization. In this study, a series of epoxide polymers doped with AIEgen tetraphenylethene (TPE) are achieved through free-radical-promoted cationic photopolymerization. Free radical photoinitiator acts as a sensitizer for the cationic photopolymerization of epoxides, and the photocuring performance of the TPE-doped photocurable resin is evaluated. UV-Vis absorption and photoluminescence spectra are characterized to investigate the AIE behavior of TPE molecules doped in the epoxy polymer. This research demonstrates that the TPE-doped cationic photocurable resin is capable of generating luminescent film and pattern fabrication, which has significant potential in anti-counterfeiting inks and other optical-functional applications.