The cure properties of naphthalene-based epoxy resin (EXA-4700) systems with different hardeners and latent catalysts were investigated. The latent catalysts used in this study were tetraphenyl phosphonium-thiocyanate (TPP-SCN) and 2-ethyl-4-methyl imidazolium tetraphenyl borate (EMZ-K). The cure kinetics of these systems were analyzed by dynamic and isothermal data from the Differential Scanning Calorimetry (DSC) experiments, and the kinetic parameters of all systems were reported in generalized kinetic equations with diffusion effects. Thermal expansion coefficients of these epoxy systems were obtained by mean of Thermo Mechanical Analyzer (TMA) measurement. The conversion reaction rate of EXA-4700 system with TPP-SCN is higher than that with EMZ-K, irrespective of the location of hydroxyl group in naphthol hardeners or the differences in cure mechanisms between these latent catalysts. The thermal expansion coefficient in low temperature region (alpha 1) of EXA-4700 resin systems with 2,7-naphthol as a hardener is lower than that with 1,6-naphthol. The cure properties of these epoxy resin systems with different hardeners and catalysts were investigated with respect to the curing molecular structure.