We show that the quasi-1D behavior of BaVS3 can be understood analyzing the X-ray absorption near edge spectra at the sulfur K edge. Linear dichroism experiments, analyzed with the help of ab initio calculations, reveal two strong and polarization dependent pre-edge features, induced by the band character of the 3d vanadium levels. They are related to crystal held split t(2g) and e(g), states. When the temperature is lowered, the t(2g) feature shifts progressively to higher energy, and its intensity increases for the polarization along the c-axis, stacking direction of the V-S face sharing octahedra. This behavior points to the depletion of sulfur states and thus the lack of S 3p-V 3d hybridization in the direction of V-S chains. (C) 2014 Elsevier BM. All rights resetved.