A tin-modified copper foam for the efficient and selective reduction of CO2 to CO is reported. We employ a cost-efficient electrodeposition route to form a three-dimensional porous dendrite architecture, in which each dendrite possesses a copper core and a copper oxide/tin oxide shell. The sparse tin species on the electrode surface play a key role to achieve excellent faradaic efficiencies for CO formation with a maximum value of 94%. We demonstrate high CO partial current densities of 4.7 mA cm(-2) and 7.9 mA cm(-2) at applied potentials of -0.8 V and -1.1 V vs. the reversible hydrogen electrode, respectively. The high activity for electrochemical CO2 reduction is attributed to the unique hierarchical porous structure, which offers abundant electrochemically active sites and facilitates mass transport.