The electronic structure and local coordination of binary (Mo₆T₈) and ternary Chevrel Phases (M_xMo₆T₈) are investigated for a range of metal intercalant and chalcogen compositions. We evaluate differences in the Mo L₃-edge and K-edge X-ray absorption near edge structure across the suite of chalcogenides M_xMo₆T₈ (M = Cu, Ni, x = 1-2, T = S, Se, Te), quantifying the effect of compositional and structural modification on electronic structure. Furthermore, we highlight the expansion, contraction, and anisotropy of Mo₆ clusters within these Chevrel Phase frameworks through extended X-ray absorption fine structure analysis. Our results show that metal-to-cluster charge transfer upon intercalation is dominated by the chalcogen acceptors, evidenced by significant changes in their respective X-ray absorption spectra in comparison to relatively unaffected Mo cations. These results explain the effects of metal intercalation on the electronic and local structure of Chevrel Phases across various chalcogen compositions, and aid in rationalizing electron distribution within the structure.