• An effective strategy has been established by doping Ce into Cu NPs to tune the electronic state of Cu. • It attains the faradaic efficiency of C 2 H 4 as high as 53% with a current density of 150 mA/cm 2 . • Such performance is about 2.8-fold increase when compared with Cu NPs. • The electronic structure regulation and defective sites facilitate highly efficient C 2 H 4 production from CO 2 electroreduction. Coupling another metal element tends to produce catalytic controls of high activity and selectivity. However, this action is still poorly explored to improve the selectivity of the electroreduction of CO 2 to C 2 H 4 with high energy density. Herein, Ce-doped Cu nanoparticles (Ce-Cu NPs) are synthesized by one-step co-reduction method and presented a preferable example that promotes selective transformation of CO 2 to C 2 H 4 in a flow-cell configuration. Thereinto, high faradaic efficiency (FE) of C 2 H 4 for Ce-Cu-2 NPs could reach 53% with the current density of 150 mA cm −2 , which is 2.8 times higher than that of Cu NPs. The outstanding performance mainly stems from tailoring the doped-Ce content shrinks particle sizes and forms oxygen defects due to the electron effect of nearby Ce atoms, boosting local electronic re-distribution of Cu. Meanwhile, in-situ Raman spectroscopies evidenced that the doping of Ce can enhance Cu site to bond *CO, which were beneficial to C–C coupling and thus endowed the catalyst with the superior catalytic performance in CO 2 electroreduction toward C 2 H 4 .