Multi-photon microscopy operating at 1550 nm is employed as a rapid characterization tool for studying the photostability of three well-known electro-optical materials. Different nonlinear optical responses such as multi-photon excitation fluoresence, second-, and third-harmonic generation can be used as detection probes to reveal the degradation mechanisms. This technique is rapid, accurate, and can be used to study the photostability of a broad range of materials.