The investigation of the cure kinetics of a diglycidyl ether of bisphenol A (DGEBA)/phenol-novolac blend system with different phenolic contents initiated by a cationic latent thermal catalyst [N-benzylpyrazinium hexafluoroantimonate (BPH)] was performed by means of the analysis of isothermal experiments using a differential scanning calorimetry (DSC). Latent properties were investigated by measuring the conversion as a function of curing temperature using a dynamic DSC method. The results indicated that the BPH in this system for cure is a significant thermal latent initiator and has good latent thermal properties. The cure reaction of the blend system using BPH as a curing agent was strongly dependent on the cure temperature and proceeded through an autocatalytic kinetic mechanism that was accelerated by the hydroxyl group produced through the reaction between DGEBA and BPH. At a specific conversion region, once vitrification took place, the cure reaction of the epoxy/phenolnovolac/BPH blend system was controlled by a diffusion-control cure reaction rather than by an autocatalytic reaction. The kinetic constants k(1) and k(2) and the cure activation energies E-1 and E-2 obtained by the Arrhenius temperature dependence equation of the epoxy/phenol-novolac/BPH blend system were mainly discussed as increasing the content of the phenol-novolac resin to the epoxy neat resin.