Hydrogen is regarded as a kind of clean energy with high caloricity and non-pollution, which has been studied by many experts and scholars home and abroad. Microwave discharge plasma shows light future in the area of hydrogen production from ethanol solution, providing a new way to produce hydrogen. In order to further improve the technology and analyze the mechanism of hydrogen production with microwave discharge in liquid, emission spectrum of hydrogen production by microwave discharge plasma in ethanol solution was being studied. In this paper, plasma was generated on the top of electrode by 2.45 GHz microwave, and the spectral characteristics of hydrogen production from ethanol by microwave discharge in liquid were being studied using emission spectrometer. The results showed that a large number of H, O, OH, CH, C2 and other active particles could be produced in the process of hydrogen production from ethanol by microwave discharge in liquid. The emission spectrum intensity of OH, H, O radicals generated from ethanol is far more than that generated from pure water. Bond of O—H split by more high-energy particles from water molecule was more difficult than that from ethanol molecule, so in the process of hydrogen production by microwave discharge plasma in ethanol solution; the main source of hydrogen was the dehydrogenation and restructuring of ethanol molecules instead of water decomposition. Under the definite external pressure and temperature, the emission spectrum intensity of OH, H, O radicals increased with the increase of microwave power markedly, but the emission spectrum intensity of CH, C2 active particles had the tendency to decrease with the increase of microwave power. It indicated that the number of high energy electrons and active particles high energy electron energy increased as the increase of microwave power, so more CH, C2 active particles were split more thoroughly.