Pyrolysis process has been considered to be an efficient approach for valorization of lignocellulosic biomass into bio-oil and value-added chemicals. Bio-oil refers to biomass pyrolysis liquid, which contains alkanes, aromatic compounds, phenol derivatives, and small amounts of ketone, ester, ether, amine, and alcohol. Lignocellulosic biomass is a renewable and sustainable energy resource for carbon that is readily available in the environment. This review article provides an outline of the pyrolysis process including pretreatment of biomass, pyrolysis mechanism, and process products upgrading. The pretreatment processes for biomass are reviewed including physical and chemical processes. In addition, the gaps in research and recommendations for improving the pretreatment processes are highlighted. Furthermore, the effect of feedstock characterization, operating parameters, and types of biomass on the performance of the pyrolysis process are explained. Recent progress in the identification of the mechanism of the pyrolysis process is addressed with some recommendations for future work. In addition, the article critically provides insight into process upgrading via several approaches specifically using catalytic upgrading. In spite of the current catalytic achievements of catalytic pyrolysis for providing high-quality bio-oil, the production yield has simultaneously dropped. This article explains the current drawbacks of catalytic approaches while suggesting alternative methodologies that could possibly improve the deoxygenation of bio-oil while maintaining high production yield.