α‐Form CoxNi1–x hydroxides with different Co/Ni ratios were synthesized by a chemical co‐precipitation method under mild conditions. The effects of Co/Ni ratio on the structure, morphology, and supercapacitive properties of α‐form CoxNi1–x hydroxides were investigated in detail. α‐Form CoxNi1–x hydroxides had structures similar to those of hydrotalcite and α‐Co(OH)2, and they exhibited better electrochemical performance than α‐Co(OH)2 on testing by XRD, FTIR, and electrochemical performance (when x ≠ 0). The highest specific capacitance at 1 A g–1 for α‐form CoxNi1–x hydroxides (for x = 0.2) is 1696.7 F g–1. An asymmetric supercapacitor packaged with Co0.6Ni0.4 hydroxide and activated carbon as positive and negative material, respectively, had an energy density of 23.5 Wh kg–1 at a power density of 412.5 W kg–1.