Synthesis of N‐propanol from CO2 Electroreduction on Bicontinuous Cu2O/Cu Nanodomains

n‐propanol is an important pharmaceutical and pesticide intermediate. To produce n‐propanol by electrochemical reduction of CO2 is a promising way, but is largely restricted by the very low selectivity and activity. How to promote the coupling of *C1 and *C2 intermediates to form the *C3 intermediate for n‐propanol formation is challenging. Here, we propose the construction of bicontinuous structure of Cu2O/Cu electrocatalyst, which consists of ultra‐small Cu2O nanodomains, Cu nanodomains and large amounts of grain boundaries between Cu2O and Cu nanodomains. The n‐propanol current density is as high as 101.6 mA cm−2 at the applied potential of −1.1 V vs. reversible hydrogen electrode in flow cell, with the Faradaic efficiency up to 12.1%. Moreover, the catalyst keeps relatively stable during electrochemical CO2 reduction process. Experimental studies and theoretical calculations reveal that the bicontinuous structure of Cu2O/Cu can facilitate the *CO formation, *CO‐*CO coupling and *CO‐*OCCO coupling for the final generation of n‐propanol.