A new polymer film destructive depth profiling protocol is presented for the analysis of photo- and thermally degraded thin films on the depth scale of less than 100 microns. The method, demonstrated here on thin films of poly(vinyl chloride) (PVC), provides a means of preparation of thin laminates of high optical quality comprised of many (>20) thin layers of individual thickness less than 15 microns. The constituent layers are fused together under appropriate pressure, temperature and time treatment to yield a film assembly of high optical quality that behaves like a uniform single layer during photodegradation exposure, but which may still be separated after treatment. Compared to previous techniques, this new method is relatively simple and non-labor intensive. Film adhesive properties are controlled to within +/-5% Concentration depth profiles of polymer photolysis products were reconstructed by analyzing each of the separated layers using UV-visible spectrophotometry. The continuity of these film assemblies with respect to mechanical properties, adhesive properties and the depth distribution of key photolysis reagents and products was confirmed using photothermal and reference microscopy techniques. Optical absorption depth profiles examined in UV- photodegraded poly(vinyl chloride) (PVC) films exhibited the classic dependencies expected in the presence of nitrogen and oxygen atmospheres.