The effects of surface treatment, particle size, and concentration of titanium dioxide (TiO2) and its dispersion on the photodegradation of two resin systems, epoxy and acrylic urethane, were examined. A suite of techniques, including laser scanning confocal microscopy (LSCM) and attenuated total reflectance -Fourier transform infrared spectroscopy (ATR-FTIR), was used to follow the degradation process of TiO2/polymer films as a function UV exposure. LSCM was used to show that both pigment dispersion and durability of the polymer matrix influenced the generation of pits/holes in pigmented polymer film. The type of pigment had a greater influence on the more durable polymer matrix, the acrylic urethane system. The epoxy system showed the greatest extent of degradation regardless of the TiO2 choice. The LCSM results were supported by the ATR-FTIR data.