We have extensively characterized the fluorescence behavior of unsaturated polyester (UP) resin in the absence and presence of a 1,3-bis-(1-pyrenyl)propane (BPP) fluorescent probe at various dynamic and isothermal cure histories by means of a steady-state fluorescence technique using a front-face illumination equipment. In addition, we explored the effect of the fluorescence intensity on the relaxation of the fluorescent probe in the UP resin by resting the dynamically and isothermally cured resin at ambient temperature and pressure for 24 h. The monomer fluorescence intensity, which has two characteristic peaks at 376 and 396 nm, changed noticeably depending on the cure temperature and time and provided important information with respect to the molecular and photophysical responses upon curing. The result of the fluorescence study indicates that the increased local viscosity and restricted molecular mobility of the UP resin surrounding the BPP probe after curing are both responsible for the enhancement of the monomer fluorescence intensity. Our results also demonstrate that once the BPP probe has enough time to rearrange and become isolated prior to fluorescence, a sufficient amount of fluorescence is emitted. Therefore, we note that the fluorescence behavior of this UP resin system is influenced strongly by the relaxation process of the fluorescent probe in the resin as well as process used to cure the resin.