In all, this work develops the first C-S coupling pathway via heterogeneous electrocatalysis using CO2 as a building block. Using Cu-based catalysts as a model system, we illustrate how CO2 is reduced to surface-bound electrophilic intermediates like *CHOH, which are then subject to nucleophilic attack by near-surface SO3 2-species, yielding three distinct C-S bond containing species. The expansion of scope of CO2 reduction to include products with C-S bonds is set to grant electrocatalytic technologies access to not only fuels and commodity chemicals, but also to important sets of fine/specialty chemicals and widen the impact of this growing domain.