In the quest to mitigate excessive CO2 emissions, the electrochemical reduction of CO2 (eCO2R) into multi-carbon fuels and vital chemical precursors emerges as a compelling strategy. Meticulous control of the C–C coupling on a catalyst surface is a grand challenge in the selective production of desired C2+ products. Ethane and propanol are among the most desirable C2+ products in the gas and liquid phase, respectively. Herein, we demonstrate facile femtosecond laser-enabled tuning of Cu selectivity towards ethane and propanol. The laser-enabled tailoring of the Cu surface induces a shift from C1 products to ethane and propanol. This shift in product composition is attributed to the concurrent creation of hierarchical porous structures, the stabilization of {111}, {200}, and {220} Cu2O facets, and the promotion of the Cu1+ oxidation state. These alterations collectively enhance the adsorption strength, leading to an increased propensity for C-C coupling and, consequently, an elevated selectivity toward C2+ products.