Waste heat recovery was considered as a promising candidate for energy conservation and emission reduction. Methanol steam reforming was considered to be an effective means for hydrogen production because of its advantages. In this work, a micro reactor was constructed and thermoelectric generation coupled with hydrogen production from methanol steam reforming was innovatively used to recycle waste heat, which was simulated by hot air from a hot air gun. The waste heat was converted into electricity and hydrogen at the same time. The characteristic of thermoelectric generation coupled with methanol steam reforming was investigated. It was experimentally verified that both the hydrogen production rate and methanol conversion increased with the increasing inlet temperature, but thermal efficiency increased firstly and then decreased with the increasing temperature. The methanol steam reforming could effectively maintain cold side temperature distribution of thermoelectric generation. In the case of the thermoelectric module (1), the highest temperature difference of 37 °C was determined and the maximum open circuit voltage of 2 V was observed. The highest methanol conversion of 64.26% was achieved at a space velocity of 0.98 h−1 when the temperature was 543 K, comprehensively considering the CO content and thermal efficiency.