In the present study, the fluorescence behavior ova phenylethynyl-terminated imide (LaRC PETI-5) resin, a bismaleimide (BMI) resin, and various LaRC PETI-5/BMI blends with different blend compositions has been characterized as a function of heat-treatment temperature, using a steady-state fluorescence technique with a front-face illumination method far solid-state films. It is observed that there are distinguishable changes in the spectral shape, size, and position of fluorescence with varying heat-treatment temperature in the pure and blend samples. The result is qualitatively explained in terms of charge transfer complex formation as well as microenvironmental change with local mobility and viscosity occurring in the LaRC PETI-5, BMI, and their blends during the cure process. The result also implies that a steady-state fluorescence technique may be a useful tool to understand the processing conditions of polyimides and their blends in the film form on the basis of their thermo-photophysical responses.