This paper deals with the investigation of the photodegradation of (2,2-(4,4′-dimethoxyphenyl)-5,6-dimethyl-[2H]-naphtho-[1,2-b]pyran in toluene solution and in polyurethane matrix. With the aim of proposing mechanisms for the photodegradation processes, a complete determination of the photoproducts' structures has been carried out using HPLC, GC/MS and direct introduction MS techniques. The different techniques allowed us to detect the production of well-known photoproducts but also the formation of new high molecular weight oxygenated derivatives. Our investigations also underline the detection of new photo-induced products that are produced by secondary oxidative pathway.