In order to investigate the potentials to improve the deposition efficiency and to functionalize the polymer-based substrates, six configurations of microparticles Sn, Zn, Al, Sn+Al2O3, Al+Al2O3, Cu+Al2O3 were cold sprayed on the substrate of Carbon Fiber Reinforced Polymer (CFRP) composites equipped with Cu-based sublayer or Al-based sublayer. The process conditions were kept unchanged. Microanalysis of sublayers and coatings was performed via a Scanning Electronic Microscope (SEM), the deposition mechanisms of different powders couplings on CFRP substrate were then discussed. The results indicated that although the deposition efficiencies were negative, the systems of Zn, Al and Al+Al2O3 perform better among all the configurations. It was found that the addition of alumina led to a lower deposition efficiency (DE), compared to the corresponding pure coatings. For single-component Sn, Zn and Al powders, they all showed an increasing trend of DE when changing the substrate from Cu-based systems to Al-based systems. The aim of this present work is to elaborate the intrinsic causes of erosion issues and to provide a reference value for picking spraying materials and preparing functionalized CFRP substrates. According to the SEM analysis, the insufficient deformation and escape behaviours of spherical copper powders explained for the difficulty of coating formation. It was noticeable that the surfaces of Al-based systems were more uniform than those of Cu-based ones, due to their desirable deformation abilities. Besides, the significant flattened particles, material mixing and melting phenomenon were observed in Al-involved systems, which would definitely contribute to the adhesive bonding between coating and substrate.