AbstractFrequency domain photopyroelectric effect spectrometry (FD‐PPES) is a recent spectroscopic technique that may be used to recover depth profiles of optical absorption in thin films on a noncontact and nondestructive basis. In this work a series of well characterized thermally homogeneous samples were prepared that exhibited continuous or discrete subsurface profiles of optical absorption. Multifrequency FD‐PPES measurements made on these samples were compared to theory using a heat transfer model, which we have developed for a multilayer thermally homogeneous absorber. Excellent agreement between experiment and theory was obtained for these model studies. While both phase and magnitude channels of the FD‐PPES response give depth profiling information, the phase response is especially sensitive to variations in the subsurface profile of optical absorption. By means of the phase response it is possible to determine the number and spatial positions of absorbers in a series of discrete absorbing layers. The FD‐PPES. technique has excellent potential for analysis and nondestructive evaluation of polyme