Electrocatalytic reduction of CO2 affords a potential way to mitigate the greenhouse effect and fuel crisis. In this work, we compared highly-dispersed CuO nanocomposites and Cu–Cu2O nanocomposites which all derived from CuxAl-LDH for CO2 electrochemical reduction. The Cu–Cu2O based nanocomposites obtained through the restoration strategies still retain its layered structure, simultaneously increasing dual Cu–Cu2O active sites, which exhibit excellent performance in selective reduction of CO2 to C2H4. The Cu5Al-ER obtained through in-situ electrochemical reduction is modified by bulk phase, which can regulate active species, increase surface active sites, enhance C–C coupling. Meanwhile, the electrochemical strategy offers numerous benefits, including gentle conditions, adjustable monitoring, exceptional efficiency and adaptability. We have confirmed that cost-effective Cu–Cu2O based nanocomposite derived from Cu5Al-LDH can effectively promote C–C coupling during electrochemical CO2 conversion and improve FEC2H4. The FEC2H4 of Cu5Al-ER reaches 36% at −1.2 V vs. RHE. And the current density reaches −172 mA·cm−2 at −1.6 V vs. RHE. The results showed that compared to Cu5Al-LDO, the FEC2H4 of Cu5Al-ER increased by 2.6 times. In addition, Cu5Al-ER exhibits excellent stability during the 12 hours CO2 catalytic reduction process.