Methanol (CH3OH) is a liquid hydrogen (H2) source that effectively releases H2and is convenient for transportation. Traditional thermocatalytic CH3OH reforming reaction is used to produce H2, but this process needs to undergo high reaction temperature (e.g., 200 °C) along with a catalyst and a large amount of carbon dioxide (CO2) emission. Although photocatalysis and photothermal catalysis under mild conditions are proposed to replace the traditional thermal catalysis to produce H2from CH3OH, they still inevitably produce CO2emissions that are detrimental to carbon neutrality. Here, we, for the first time, report an ultrafast and highly selective production of H2without any catalysts and no CO2emission from CH3OH by laser bubbling in liquid (LBL) at room temperature and atmospheric pressure. We demonstrate that a super high H2yield rate of 33.41 mmol·h−1with 94.26% selectivity is achieved upon the laser-driven process. This yield is 3 orders of magnitude higher than the best value reported for photocatalytic and photothermal catalytic H2production from CH3OH to date. The energy conversion efficiency of laser light to H2and CO can be up to 8.5%. We also establish that the far from thermodynamic equilibrium state with high temperature inside the laser-induced bubble and the kinetic process of rapid quenching of bubbles play crucial roles in H2production upon LBL. Thermodynamically, the high temperature induced using laser in bubbles ensures fast and efficient release of H2from CH3OH decomposition. Kinetically, rapidly quenching of laser-induced bubbles can inhibit reverse reaction and can keep the products in the initial stage, which guarantees high selectivity. This study presents a laser-driven ultrafast and highly selective production of H2from CH3OH under normal conditions beyond catalytic chemistry.