Alkali metal sulfur redox chemistry offers promising potential for high-energy-density energy storage. Fundamental understanding of alkali metal sulfur redox reactions is the prerequisite for rational designs of electrode and electrolyte. Here, we revealed a strong impact of alkali metal cation (Li+, Na+, K+, and Rb+) on polysulfide (PS) stability, redox reversibility, and solid product passivation. We employed operando UV-vis spectroscopy to show that strongly negatively charged short-chain PS (e.g., S42-/S32-) is more stabilized in the electrolyte with larger cation (e.g., Rb+) than that with the smaller cation (e.g., Li+), which is attributed to a stronger cation-anion electrostatic interaction between Rb+ and S42-/S32- owing to its weaker solvation energy. In contrast, Li+ is much more strongly solvated by solvent and thus exhibits a weaker electrostatic interaction with S42-/S32-. The stabilization of short-chain PS in K+-, Rb+-sulfur cells promotes the reduction of long-chain PS to short-chain PS, leading to high discharge potential. However, it discourages the oxidation of short-chain PS to long-chain PS, leading to poor charge reversibility. Our work directly probes alkali metal-sulfur redox chemistry in operando and provides critical insights into alkali metal sulfur reaction mechanism.