AlxCoCrFeNi high-entropy alloys with different Al contents (x in molar ratio, x = 0 – 2.0) were prepared by electrochemical process using the mixed metal oxides as the precursor. The effects of Al addition on the crystal structure, microstructure, mechanical property and corrosion behavior were investigated by XRD, XPS, SEM, FE-EPMA, universal tensile testing machine, Vickers hardness tester and electrochemical workstation. With the increase of Al contents, the crystal structure of AlxCoCrFeNi HEAs transformed from FCC to the mixed crystal structures of FCC and BCC, finally, to BCC + B2. The σ-phase was formed in AlxCoCrFeNi (x = 0.8 – 1.5) HEAs during the electrolysis deoxidization. The bulk HEAs could be prepared successfully via vacuum hot pressing sintering process. The bulk HEAs exhibit excellent ultimate tensile strength (UTS) and hardness. The hardness of the Al0 (245.2 HV) HEA and Al0.3 (261.2 HV) HEA was twice high of the sample prepared by arc-melting method. Compared with 304 stainless steel (304SS) and AlxCoCrFeNi HEAs prepared by other method, AlxCoCrFeNi HEAs prepared by the united process shows a comparable corrosion resistance in acid, alkali and salt aqueous solutions.