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The developing human societies are being faced provoking energy crises due to higher demands of energy for increasing worldwide populations. The massive depletion of natural resources and global warming issues sound a laud alarm for modern societies. Methanol is attracting huge attractions as an alternative fuel in direct methanol fuel cells for the development of future energy conversion resources, while the fast chemisorptions of methanol and stable performance remained a challenge thereby hampering their scalable applications at commercial level. Herein, we focused on these goals by alteration in chemistry of materials being used as anode catalysts for direct methanol fuel cells. The promising PtPd alloy nanoparticles with tailored compositions are loaded on highly conductive rGO-CNTs support material. The highly active components of the metals and powerful electron transfer material as a support, these combined characteristics in one nanostructure facilitate the fast chemisorptions of methanol with durable performance. The ex-situ electrochemical and in-situ online differential electrochemical mass spectrometric analysis reveal the enhanced electrocatalytic methanol oxidation reaction activities attribute towards direct chemisorptions intermediate pathways introduced via geometric and structural factor within nanocomposite material.