Different mole ratios (  :  =  : ) of hybrid copper-nickel metal hexacyanoferrates (Cu Ni HCFs) were prepared to explore their morphologies, structure, electrochemical properties and the feasibility of electrochemical adsorption of cobalt ions. Cyclic voltammetry (CV), field emission scanning electron microscopy (FE-SEM), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) indicated that the  :  ratio of Cu Ni HCF nanoparticles can be easily controlled as designed using a wet chemical coprecipitation method. The crystallite size and formal potential of Cu Ni HCF films showed an insignificant change when 0 ≤  :  < 0.3. Given the shape of the CV curves, this might be due to Cu ions being inserted into the NiHCF framework as countercations to maintain the electrical neutrality of the structure. On the other hand, crystallite size depended linearly on the  :  ratio when  :  > 0.3. This is because Cu tended to replace Ni sites in the lattice structure at higher molar ratios of  : . Cu Ni HCF films inherited good electrochemical reversibility from the CuHCFs, in view of the cyclic voltammograms; in particular, CuNiHCF exhibited long-term cycling stability and high surface coverage. The adsorption of Co fitted the Langmuir isotherm model well, and the kinetic data can be well described by a pseudo-second order model, which may imply that Co adsorption is controlled by chemical adsorption. The diffusion process was dominated by both intraparticle diffusion and surface diffusion.