Steady state fluorescence (SSF) technique conjunction with optical microscopy were used to study the morphology of polystyrene (PS)/poly(methyl methacrylate) (PMMA) blend upon annealing above glass transition in elevated time intervals. The PS/PMMA blends were prepared from dissolution of pyrene (P) and naphthalene (N) labeled PS and PMMA particles, respectively. Monte Carlo Simulations were performed to model the N and P fluorescence intensities (I-N and I-P), Using photon diffusion theory. Number of N and P photons (N-N and N-P) emerging from the front surface of the blend are calculated when only N is excited, where N-P photons are combined of photons from radiative (N-PR) and nonradiative (N-PNR) energy transfer processes. Optical microscopy images were taken at each annealing step to Support Our findings from fluorescence measurements. (c) 2006 Wiley Periodicals, Inc.