A method is suggested that allows separation of the contributions from homogeneous and inhomogeneous broadening (IB) to a total spectral contour of rigid systems. Based upon a simple convolution model of inhomogeneous broadening, the method allows calculation of homogeneously broadened spectra and an inhomogeneous distribution function (IDF) from the measured excitation-wavelength-dependent fluorescence spectra of the system. The method is applied successfully to the solid solution of coumarin 334 (C334) in poly(methyl methacrylate) (PMMA) glass at 293 K.