Polylactide (PLA) based nanocomposites of organically modified montmorillonite and micro-talc based microcomposites were prepared with different compositions and were UV-light irradiated under artificial accelerated conditions representative of solar irradiation. The chemical modifications resulting from photo-oxidation were followed by infrared (IR) and ultraviolet (UV)-visible spectroscopies. The infrared analysis of PLA photooxidation shows the formation of a band at 1847 cm–1 due to the formation of anhydrides. The filler addition provokes an increase of anhydride formation rate dependent on filler nature, amount and dispersion degree on the matrix. The main factors that influence oxidation rate are the total extension of polymer/filler interfacial area and the presence of transition metal impurities of clays.