The work aims to prepare a series of free radical-cationic hybrid light-curing inkjet inks with seven different kinds of acrylate, alicyclic epoxy monomer 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxycyclohexylmethyl ester (TTA-21), photoinitiator, and color paste as raw materials and study the effects of acrylate type, acrylate dosage, and ratio of photoinitiators on the light-curing behavior and the cured film properties (adhesion, hardness and thermal performance) of the hybrid inkjet ink. The real-time infrared spectra were used to characterize the polymerization kinetics of the ink of the hybrid light-curing system, and a synchronized thermal analyzer (TGA) was used to characterize the heat resistance of the hybrid system. The hardness and adhesion of the cured film were tested by the hundred-grid method and a pencil hardness tester. The polymerization kinetics of the ink in a radical-cationic hybrid light-curing system was related to the system viscosity, radical structure, and other factors. The hybrid system viscosity was low, the mobility of the chain increased, and the kinetics of the reaction were improved. Furthermore, the internal stress, and brittleness of the cured film increased with increasing acrylate functionalities, enhancing the heat resistance of the system and resulting in low hardness and poor adhesion of the cured film. The bifunctional HDDA/TTA-21 hybrid system has lower viscosity, faster light curing speed, higher conversion of double bonds and epoxy groups, leading to better comprehensive performance of the cured film. The HDDA/TTA-21 hybrid system satisfies soldermask process requirements and is potentially promising for application in inkjet soldermasks.