In the present study the cure behavior of diglycidyl ether of bisphenol-A(DGEBA) using an anhydride-based hardener in the presence of N,N-dimethyl benzyl amine (BDMA) or 1-cyanoethyl-2-ethyl-4-methyl imidazole (2E4MZ-CN) as an accelerator has been monitored and interpreted from the viewpoint of photophysical properties by means of fluorescence spectroscopy. To do this, 1,3-bis-(1-pyrene)propane (BPP) was well incorporated in the epoxy resin system by mechanical blending. The BPP probe, which is very sensitive to conformational change of the molecule influenced by the surrounding medium, successfully formed intramolecular excimer fluorescence. It is susceptible to the micro-viscosity or local viscosity and molecular mobility according to the epoxy cure. The cure behavior was explained with monomer fluorescence intensity ($I_{M}$ ), excimer fluorescence intensity ($I_{E}$ ) and $I_{M}$ /$I_{E}$ ratio as a function of cure time, cure temperature and accelerator. The present work agreed with the previous report on the cure behavior of an epoxy-anhydride system studied using DSC or torsion pendulum method. This study also suggests that the use of fluorescence technique may provide information on cure behavior of a thermosetting resin in a low temperature region, which has not been well interpreted by other analytical methods.