The rare-earth based molybdenum chalcogenides, REMo6Se8 (RE = rare-earth metals) have been extensively studied because of their unique crystal structure based on Mo6Se8 clusters and their outstanding properties involving coexistence of superconductivity and magnetism. Among all these compounds, Ce and Eu based chalcogenides are magnetic and non-superconductors and possess many novel properties. Understanding their electronic structure is likely to provide valuable information about these materials. We employ X-ray absorption near-edge structure (XANES) spectroscopy at Mo and Se K-edges of EuMo6Se8 to identify the local environment respectively around Mo and Se ions and XANES spectra at L3-edge of Eu ion to identify their valence state. Results from this study demonstrate that Se ions in EuMo6Se8 are in two inequivalent sites and the valency of Eu is divalent.