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Electric heating is frequently employed to treat volatile organic compounds (VOCs) through catalytic combustion. However, it is associated with problems such as slow heating, high energy consumption, and low efficiency. This study explores PdPt/Al₂O₃ catalysts for igniting methanol (MeOH) through H₂ catalytic combustion, providing internal on-site heating of catalyst active sites. It also investigates VOCs’ abatement using H₂-ignited-MeOH combustion without H₂ and external heating. Bimetallic catalysts enhance activity and reduce thermal aging. Hydrogen gas (H₂) can initiate the MeOH combustion at room temperature with the addition of very small amounts, even below its low explosive limit of 4%. This process optimizes MeOH ignition at approximately 350 °C, even when the concentration of H₂ is as low as 0.01%. This method enhances combustion kinetics, converting MeOH and VOCs into CO₂ and water. Catalytic performance is independent of PdPt nanoparticle sizes in fresh and spent catalysts, represented in XRD and STEM. Using hydrogen as an igniting agent provides a clean, effective method to initiate catalytic reactions, addressing traditional challenges and enhancing VOCs’ decomposition efficiency.