The electrosynthesis of higher-order alcohol from C1-based flue gas (CO2/CO) is desired to addresses the need for long-term storage of renewable electricity; unfortunately, present-day performance remains far below that needed for practical applications. Engineering copper-based catalysts that favor high-value alcohols is desired in view of the energy density, ready transport, and established use of these liquid fuels. In this talk, we report a class of core-shell-vacancy engineering catalysts that utilize sulfur atoms in the nanoparticle core and copper vacancies in the shell to achieve efficient electrochemical CO2 reduction to ethanol and propanol. These catalysts shift selectivity away from the competing ethylene reaction and toward liquid alcohols. We achieve a C2+ alcohol production rate of 126mA cm-2 with a selectivity of 32% Faradaic efficiency; we further report a catalyst design strategy that promotes C3 formation via nanoconfinement of C2 intermediates, promoting thereby C2:C1 coupling inside a reactive nanocavity. The nanocavities show a morphology-driven shift in selectivity from C2 to C3 products in the carbon monoxide electroreduction, reaching propanol Faradaic efficiency of 21% at a conversion rate of 7.8mA cm-2.