Solvent shift and inhomogeneous broadening of optical transitions in condensed matter are direct consequences of the dye‐matrix interaction. According to a stochastic theory, the ratio between the solvent shift and the width of an inhomogeneous distribution, and also its shape, depend on the average distance between the matrix units as compared to the size of the dopant molecules. In this way the nearly Gaussian shape of most absorption bands and the Lorentzian shape of spectral‐diffusion kernels can be explained within the framework of the same model. By performing site‐selective spectroscopic experiments at different frequencies within an absorption band it is possible to obtain more detailed information on the internal structure of the inhomogeneous distribution. Electric‐field studies of persistent spectral holes, for instance, show that in weakly polar systems, the solvent shift is mainly determined by the van der Waals interaction.