An electrochemical cell and method for reducing carbon dioxide and/or dehydrogenating a hydrocarbon to an olefin are provided. The electrochemical cell includes a cathode having a first conducting component that is active toward adsorption and reduction of an oxidizing agent such as CO2; and an anode having a second conducting component that is active toward adsorption and oxidation of a reducing agent such as a hydrocarbon. Additionally, a hydrophobic modifier is present on at least a portion of a surface of the second conducting component or both the first and second conducting components. The method includes exposing the cathode to a CO2-containing fluid; exposing the anode to a hydrocarbon-containing fluid; and applying a voltage between the cathode exposed to the CO2-containing fluid and the anode exposed to the hydrocarbon-containing fluid, wherein the voltage is sufficient to simultaneously oxidize the hydrocarbon via a dehydrogenation reaction and reduce the CO2.