A new technique based on steady state fluorescence (SSF) measurements is introduced for studying dissolution of polymer films. These films are formed from naphthalene (N) and pyrene (P) labeled poly(methyl methacrylate) (PMMA) latex particles, sterically stabilized by polyisobutylene (PIB). Annealing was performed above T-g,at elevated temperatures for 30 min time intervals for film formation. Film formation from these latexes is monitored by the extent of energy transfer from N to P using SSF and by the transmitted photon intensity from these films using UV visible (UVV) methods. Desorption of P labeled PMMA chains was monitored in real-time by the change of pyrene fluorescence intensity. Dissolution experiments were performed in various solvents with different solubility parameters, delta, at room temperature. Diffusion coefficients, D, in various solvents were measured and found to be around 10(-) (10) cm(2)/s. Strong relationships between D and delta were observed. Diffusion activation energy was measured by performing dissolution experiments in toluene-heptane mixtures at elevated temperatures and determined to be 24.4 kcal mol(-1).