Abstract: Biomass, as a renewable energy source, features wide availability, multiple functions, and carbon neutralization. The high-value resource utilization of biomass is conducive to reducing reliance on high-carbon fossil energy, ensuring national energy security, and curbing environmental pollution, aligning with the needs of China's "dual carbon" national strategy. Pyrolysis, as the foundation of biomass thermochemical conversion, is one of the best technologies to achieve a high-value utilization of biomass energy. However, it has some core issues such as low bio-oil yield and poor quality. To overcome these problems, a cryogenic technology was innovatively applied to the field of biomass pyrolysis, and a new biomass oil production method of "cryogenic + fast pyrolysis" was proposed to increase the yield and quality of pyrolytic bio-oil. Taking two types of crop straw as experimental research objects, the rapid freezing pretreatment method with liquid nitrogen was adopted to study the evolution mechanism of the product distribution and composition of biomass pyrolysis under cryogenic pretreatment. The experiments show that compared with conventional pyrolysis, the increase in the bio-oil yield after cryogenic pretreatment of biomass pyrolysis can reach 14.16% to 23.73%, and the cryogenic pretreatment temperature has a positive correlation with the bio-oil yield, and the maximum bio-oil yield (22.3% to 26.3%) is reached at −90 ℃, exceeding the bio-oil yield of the aluminum method by 8.50% to 22.71%. The cryogenic pretreatment has a significant transformation effect on the composition of the bio-oil, and the content of benzene series (BTEX) and phenolic substances in the bio-oil composition increases significantly, with the maximum increase of 43.61% and 12.45%, respectively. The cryogenic pretreatment of liquid nitrogen inhibited the release of CO₂ and CO in biomass pyrolysis gas, and the proportion of components decreased by 7.2%−29.7%. In addition, the inhibition of the release of CO₂ and CO in the biomass pyrolysis gas and the increase of CH₄ and H₂ by cryogenic pretreatment increase by 0.2% to 14.7%. Moreover, the increase in C content and the decrease in O content in the solid product under cryogenic pretreatment are conducive to improving the combustibility of biochar and reducing its risk of spontaneous combustion.