There is compelling evidence that the degradation kinetics of thin polymer films differ significantly from bulk materials, as interfacial effects become dominant. Therefore, it is crucial to investigate these kinetics separately. Qualitative analytics of thin film degradation exist, for example, by scanning electron microscopy or atomic force microscopy, but more quantitative studies are missing. In this work, the aliphatic poly(sebacic anhydride) (PSA) is used as a model system for a quantitative degradation study. The degradation of PSA films is monitored by ellipsometry, surface‐plasmon resonance spectroscopy (SPR), and Fourier transform infrared spectroscopy (FTIR). Two kinetic regimes are observed when plotting the relative layer thickness determined by ellipsometry and SPR against the degradation time, which corresponds to two different rates of erosion. The data obtained by FTIR show a single process corresponding to the rate of anhydride bond cleavage. Overall, the degradation rate constants of PSA determined by the different methods are consistent. They are constant for PSA films with up to 378 nm thickness. Several thicker free‐standing samples are studied gravimetrically and have a degradation rate constant that is one order of magnitude lower, thus confirming thickness‐dependent degradation rate constants for poly(sebacic anhydride).