Light absorption by a solid material and conversion of part, or all, of the optical energy into heat due to nonradiative deexcitation processes within the solid can give rise to an electrical signal in a pyroelectric thin film in contact with the sample. This effect forms the basis of a new spectroscopic technique for the study of condensed phase matter. A one‐dimensional theory is presented, which describes the dependence of the pyroelectric signal on the optical, thermal, and geometric parameters of the solid/pyroelectric system. Specifically, the theory examines the conditions under which the photopyroelectric signal exhibits a linear dependence on the optical absorption coefficient of the solid. Thus a theoretical basis for the technique of photopyroelectric spectroscopy is established. Qualitative comparisons between predictions of the theory and preliminary experimental observations are used to test the applicability of the theory to experimental configurations of practical interest.