Recently, our lab and others in the field has shown the capacity for electrochemical C-N bond generation using CO2 and small molecule N-sources (e.g. N2, NO3 -, NO2 -, NH3…). These reactions primarily proceeded through the reduction of CO2 to form an activated electrophilic intermediate and subsequent coupling with a (near-)surface N-containing nucleophile. This extension of electrochemical routes enabled the build-up of higher-value, complex products than those simply available through CO2 reduction. With this in mind, we hypothesized that C-S coupling should also be possible through a similar pathway as sulfur and nitrogen should have similar properties from the diagonal relationships found within the periodic table. Thus, we moved to translate our methodology to C-S bond formation in a similar reaction setup. As a starting point, we used Cu-based catalysts 26 as a model system to generate activated electrophilic intermediates from CO2 and SO3 2-as a representative S-based nucleophile (Fig. ). Doing so, we established new reaction pathways to hydroxymethane sulfonate (HMS), sulfoacetate (SA) and methane sulfonate (MS) products via electrochemical C-S coupling with up to 9.5% Faradaic efficiency (FE). These products have use as cement additives and membrane components (SA), electrolytes and agents in organic synthesis (MS), and within various facets of the textile industry (HMS). To investigate the reaction pathway and extract out mechanistic insights translatable to future works, we carried out a combination of operando experiments (performed while the reaction was occurring) and computation modelling which pointed to *CHOH coupling to SO3 2-as a likely rate-limiting step. Crucially, this work introduces C-S bond formation in an expansion of the scope of sustainable electrosynthesis and opens up potential avenues for C-S chemical production from abundant sources and powered via renewable electricity.