Anatase, rutile and mixed anatase-rutile TiO2 are synthesized using a single pot sol-gel technique followed by variation of calcination temperature. The Pt decorated synthesized catalysts have been characterized by diffraction, spectroscopic and microscopic analyses. The cyclic voltammetry (CV) study reveals the increase of forward peak current density of methanol oxidation in alkali on Pt-anchored mixed-phase TiO2 (Pt/ARTiO2) (324.8 A g−1) by 4 and 2.5 times than that on Pt-containing rutile and anatase phases. The charge transfer conductance of the former electrode (1/184 Ω−1) is 5.7 and 8.7 times greater compare to that of the laters. The phase-dependent electrocatalytic activity of the electrodes and large retention (95%) of maximum peak current density at 500th CV cycle for the best electrode, are analyzed by different product selectivity of the electrodes. Pt/ARTiO2 is found to be the best current provider and reliable as it accelerates the formation of formate instead of carbonate.