The product selectivity in the electrochemical reduction of carbon dioxide depends on the structure of the copper electrode. Cube-shaped copper catalysts, enclosed by {100} terraces, {110} edges, and {111} corners, exhibit a size-dependent enhanced only selectivity toward C-2 products and ethylene in particular. However, the underlying chemical reasons for such a behavior are not fully understood. This computational work toward ethylene formation investigates the carbon dioxide electroreduction mechanism over copper nanocubes. The analysis of the different pathways illustrates that the thermodynamic picture is limited in describing the formation of this product. Based on the activation barriers associated with the limiting C-2 formation step, we identify a dual-facet mechanism occurring at the interface between the {100} terraces and {110} edges. These results highlight that the reactivity of shape-controlled nanocatalysts goes beyond the facet-selectivity observed in single crystals owing to the possible synergies arising at the intersection between the enclosing crystalline planes.