In this work, we implement a facile microwave-assisted synthesis method to yield three binary Chevrel-Phase chalcogenides (Mo₆X₈; X = S, Se, Te) and investigate the effect of increasing chalcogen electronegativity on hydrogen evolution catalytic activity. Density functional theory predictions indicate that increasing chalcogen electronegativity in these materials will yield a favorable electronic structure for proton reduction. This is confirmed experimentally via X-ray absorption spectroscopy as well as traditional electrochemical analysis. We have identified that increasing the electronegativity of X in Mo₆X₈ increases the hydrogen adsorption strength owing to a favorable shift in the p-band position as well as an increase in the Lewis basicity of the chalcogen, thereby improving hydrogen evolution reaction energetics. We find that Mo₆S₈ exhibits the highest hydrogen evolution activity of the Mo₆X₈ series of catalysts, requiring an overpotential of 321 mV to achieve a current density of 10 mA cm^–2_ECSA, a Tafel slope of 74 mV per decade, and an exchange current density of 6.01 × 10^–4 mA cm^–2_ECSA. Agreement between theory and experiment in this work indicates that the compositionally tunable Chevrel-Phase chalcogenide family is a promising framework for which electronic structure can be predictably modified to improve catalytic small-molecule reduction reactivity.