The effect of cobalt precursor on the structure of Co supported multi-walled carbon nanotubes (MWCNTs) were studied by using X-ray photoelectron spectroscopy (XPS). MWCNTs were treated with a mixture of nitric and sulfuric acids and decorated with cobalt and/or cobalt oxides via aqueous impregnation solutions of cobalt nitrate or cobalt acetate followed by reduction in hydrogen. XPS was mainly used to investigate the phase of cobalt on MWCNTs after reduction with H2 flow at 400℃ for 2 h. Higher cobalt-nanoparticle dispersion was found in the MWCNTS prepared via cobalt nitrate decomposition. A typical XPS spectrum of Co 2p showed the peaks at binding energy (BE) values equal to 781 and 797 eV, respectively. It is found that cobalt nitrate supported MWCNTs is more dispersive and have catalytic activity than that of cobalt acetate supported MWCNTs at same preparation condition such as concentration of precursor solution and reduction environment.