PtCo/MNC and PtCo/rGO as anodic electrocatalysts (20 wt% Pt loading) have been synthesized by non-sequential co-impregnation method and chemical reduction route using citric acid and Ar-H₂ static atmosphere. Micro-/nano-structured carbon (MNC) sample was synthesized via nanocasting process with anhydrous pyrolysis at 800 °C using SBA-15 as hard template and refined sugar as carbon source. SBA-15 was prepared via sol gel using pluronic P-123 as surfactant. GO was prepared via Hummers modified method. The prepared materials were characterized by means of N₂ physisorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and high resolution transmission electron microscopy (HRTEM). The performance of PtCo/MNC for methanol oxidation reaction (MOR) was measured by cyclic voltammetry (CV), chronoamperometry (CA). The electrochemical characterization techniques revealed that the mass activity of PtCo/MNC, PtCo/rGO and the commercial electrocatalyst PtRu/C at 20 cycles were 473, 322 and 300 mA/mg_Pt respectively as well as the carbon monoxide tolerance index I_CO for these catalysts were 1.38, 1.56 and 0.93 respectively. PtCo/rGO exhibit better electrocatalytic performance, electrochemical stability and best resistance to carbonaceous intermediates species for the electro-oxidation of methanol.