Organic electrochemistry has emerged as a modern and efficient field that represents a green methodology within synthetic organic chemistry. There are various eco-friendly and sustainable electrochemical approaches for functionalizing C–H and N–H moieties via the SO2 functional group. Organosulfone and sulfonamide derivatives, two bioactive compounds, can be synthesized via electrochemical reduction and oxidation in batch and flow systems. In this review, the pioneering and previous research studies have been reported in four sections. As such, mechanisms (anodic and cathodic reactions), effective parameters, designed cells, and isolated yields have been presented in detail.