The effect of the plating voltage on the surface roughness, morphology, chemical composition and wettability of the Ni coatings was investigated by means of Laser scanning confocal microscopy, scanning electronic microscope, X-ray diffraction, energy-dispersive spectroscopy, and water contact angle measurements. The results indicate that the evolution of surface morphology on Ni coatings prepared by brush-plating depends strongly on the variation of plating voltage. The microstructure characterization shows that the typical hierarchical cauliflower-like structures was formed uniformly on the as-prepared Ni coatings. The combination of the porous morphology and hierarchical cauliflower-like structures plays a crucial role in improving the hydrophobic property. In absence of surface chemical modification, the Ni coatings exhibit an excellent hydrophobicity and have a high contact angle of 141 degree. Based on the Cassie-Baxier models, the relationship of two dimensionless geometrical parameters and the wetting property of the Ni coatings were investigated. It was demonstrated that to obtain the stable Cassie hydrophobic state, the aspect ratio and the water contact angle on the basal surface should be as large as possible and the spacing factor should be limited within a specific range for given aspect ratio and water contact angle on the basal surface.