The Platinum catalysts on the carbon nanotubes(CNTs) supports of various diameters were prepared by wet impregnation method using H2PtCl6 precursor. The samples using 100nm, 15~20nm, 10~15nm and 5~10nm diameters of CNTs and carbon nanofibers(CNFs) are named Pt/t- CNFs, Pt/MWNTs20, Pt/MWNTs10 and Pt/MWNTs5, respectively. The effects of CNTs diameter on the Pt particle size and distribution were investigated by the means of powder XRD and TEM observation. In addition, the electro-catalytic characteristics for methanol electro-oxidation were estimated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques. The average size of Pt particles increases as follows; Pt/MWNTs10 < Pt/MWNTs5 < Pt/MWNTs20 < Pt/t-CNFs. The electro-catalytic characteristics of Pt/MWNTs10 and Pt/MWNTs20 are found to be superior in comparison with the others. For preparation of the most effective supported Pt catalyst, the optimum diameter of CNTs support in the range of 10-20nm, is needed.