Electrochemical conversion of CO 2 to valuable fuels is appealing for CO 2 fixation and energy storage. The Cu-based catalysts feature unique superiorities, but achieving high ethylene selectivity is still restricted. In this study, we propose the anchoring of an ionic liquid (IL) on a Cu electrocatalyst for improving the electrochemical CO 2 reduction to ethylene. In a water-based electrolyte and a commonly used H-type cell, a high ethylene Faradaic efficiency of 77.3 % was achieved at À 1.49 V (vs. RHE). Experimental and theoretical studies reveal that an IL can modify the electronic structure of a Cu catalyst through its interaction with Cu, making it more conducive to *CO dimerization for ethylene formation.