This article focuses on the nanoparticle electrocatalytical action on electrodeposition of nickel and the chemical combination state between nanoparticles and matrix metal in composite coating. The electrochemical behavior, from common and composite brush electroplating solution, is investigated by cyclic voltammetry. The interaction between nanoparticles and matrix metal nickel is researched by X-Ray Photoelectron Spectrometry (XPS). The microstructure and morphology of coating are observed with Transmission Electron Microscope (TEM) and Scanning Electron Microscope (SEM). The results show that nanoparticles not only can obviously induce the increasing of the current efficiency and decreasing of overpotential, but also can distinctly refine the metal crystal grains of composite coating. The experimental results demonstrate that nanoparticles take part in the electrode reaction and can evidently catalyze nickel electrodeposition. Part of the unsaturated oxygen atoms on nanoparticles surface can combine with some of the absorbed nickel atoms and form nickel-oxygen chemical bonds. There is chemical binding interaction at the interface between nanoparticles' surface and matrix metal nickel.