Gas‐liquid‐solid triple‐phase interfaces (TPI) are essential for promoting electrochemical CO2 reduction, but it remains challenging to maximize their efficiency while integrating other desirable properties conducive to electrocatalysis. Herein, we report the elaborate design and fabrication of a superhydrophobic, conductive, and hierarchical wire membrane in which core–shell CuO nanospheres, carbon nanotubes (CNT), and polytetrafluoroethylene (PTFE) are integrated into a wire structure (designated as CuO/F/C(w); F, PTFE; C, CNT; w, wire) to maximize their respective functions. The realized architecture allows almost all CuO nanospheres to be exposed with effective TPI and good contact to conductive CNT, thus increasing the local CO2 concentration on the CuO surface and enabling fast electron/mass transfer. As a result, the CuO/F/C(w) membrane attains a Faradaic efficiency of 56.8 % and a partial current density of 68.9 mA cm−2 for multicarbon products at −1.4 V (versus the reversible hydrogen electrode) in the H‐type cell, far exceeding 10.1 % and 13.4 mA cm−2 for bare CuO.