The mechanism of how interfacial wettability impacts the CO2electroreduction pathways to ethylene and ethanol remains unclear. This paper describes the design and realization of controllable equilibrium of kinetic-controlled *CO and *H via modifying alkanethiols with different alkyl chain lengths to reveal its contribution to ethylene and ethanol pathways. Characterization and simulation reveal that the mass transport of CO2and H2O is related with interfacial wettability, which may result in the variation of kinetic-controlled *CO and *H ratio, which affects ethylene and ethanol pathways. Through modulating the hydrophilic interface to superhydrophobic interface, the reaction limitation shifts from insufficient supply of kinetic-controlled *CO to that of *H. The ethanol to ethylene ratio can be continuously tailored in a wide range from 0.9 to 1.92, with remarkable Faradaic efficiencies toward ethanol and multi-carbon (C2+) products up to 53.7% and 86.1%, respectively. A C2+Faradaic efficiency of 80.3% can be achieved with a high C2+partial current density of 321 mA cm−2, which is among the highest selectivity at such current densities.