Vinyl sulfonates are vital intermediates in organic synthesis, serving as versatile electrophiles in various cross-coupling reactions. Despite their significance, direct methods for synthesizing vinyl sulfonates from styrenes have been limited. In this study, we introduce an innovative electrochemical approach that leverages bromine radical mediation to facilitate the direct synthesis of vinyl sulfonates, cheap nBu4NBr acts as both an electrolyte and a catalytic amount. This process involves the reaction of styrenes with sodium sulfinates and water under electrochemical conditions, offering a straightforward pathway to these compounds. The developed strategy is characterized by its high efficiency, operational simplicity, and environmentally benign nature, adhering to the principles of green chemistry while ensuring high atom economy and remarkable regioselectivity. Furthermore, this methodology proves effective for gram-scale synthesis and allows for the subsequent functionalization of vinyl sulfonate products with pharmaceutical derivatives, thus broadening the potential applications of electrochemical techniques in styrene functionalization.