Chalcogenide-based frameworks are Earth-abundant, stable in aqueous environments, exhibit structural flexibility and can be accessed through rapid synthesis methods, thus providing an ideal platform to investigate composition-structure-function relations to bridge synthetic tunability with catalytic performance. Within a particular subset - known as Chevrel Phases (CP) - we have identified a crucial metal-to-ligand-charge-transfer (MLCT) phenomenon in which metal intercalants donate electron density to extended periodic crystal frameworks. However, there remains a significant knowledge gap regarding how variations in metal identities and stoichiometries within these frameworks affect the electronic structure, particularly the localization of electron density on favorable binding sites for small molecule electrocatalysis, specifically for CO2 reduction (CO2R), hydrogen evolution reaction (HER), and oxygen evolution reaction (OER).