Hydrogen production from methanol has attracted substantial interest because of the clean combustion of hydrogen and the convenience of methanol in storage and transportation. However, it requires high-temperature and high-pressure conditions to reform methanol with water to hydrogen with high turnover frequency (TOF, e.g. 104 moles of hydrogen per mole of Pt per hour). Here we show that hydrogen can be produced from anhydrous alkaline methanol with a remarkable TOF of 1.8×106 moles of hydrogen per mole of Pt per hour on a light-triggered multi-layer system under mild conditions. The performance is attributed to the use of anhydrous methanol as both the proton source and the hole scavenger in alkaline conditions. In contrast to a slurry system, we show that the proposed multi-layer system avoids particle aggregation, and it leads to the effective utilization of methanol, light and Pt active sites. This notable performance steps forward to the practical light-triggered hydrogen generation.