X-ray absorption measurements in the low (pseudo-rutile) and high (rutile) temperature phases of VO2 are described. Investigations are made versus temperature and polarization. The analysis of the results leads to conclusions concerning the scattering mechanisms at the origin of the pre-edge, the edge, and the first peak of the edge. Specifically, the angular dependence of the pre-edge of the monoclinic form is different from the rutile form. A new peak on the edge appears for e ‖ cr at low temperature and the pre-edge and the first peak appears to be sensitive to the asymmetry of the local environment.