This work thoroughly investigated the electrochemical corrosion behaviors of Cu-14Fe-(0, 0.05) Ce alloys. Experimental findings revealed that the addition of Ce did not change the phase constituent, but refined α-Fe phase particle from 0.30 ± 0.04 to 0.22 ± 0.03 μm and increased its content from 1.24% to 2.17%. With the increase of corrosion time, adding Ce could increase the linear polarization resistance by up to 3 times, and correspondingly the corrosion rate was reduced to half. Moreover, Ce addition contributed to the densification of corrosion products. The α-Fe phase preferentially underwent anodic dissolution reaction, generating corrosion product Fe2O3. The increase of soaking time resulted in the occurrence of anodic dissolution of Cu-matrix phase, along with the formation of Cu2O and Cu2Cl(OH)3.