ABSTRACTThe impact of chitosan on the natural weathering behavior of two blends obtained by mixing either polyethylene (PE) with chitosan or PE, chitosan and polyethylene‐graft‐maleic anhydride (PEgMA) as a compatibilizer is analyzed. In order to follow the weathering behavior of both the uncompatibilized and compatibilized systems, the blend films are exposed to outdoor conditions for 6 months. The weathering behavior of the films is monitored by mechanical tests, spectroscopic Fourier transform infrared, and morphological analyses at different weathering periods of time. The presence of chitosan in the blends accelerates significantly the degradation of the films. Apparently, PEgMA also accelerates the photo‐oxidation rate of the films. This behavior appears to be related to the photo‐oxidative instability of maleic anhydride, and also to the better dispersion of chitosan in the PE matrix, which is due to the interactions in the PE/chitosan interface caused by the addition of the compatibilizer. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41045.