Increasing fossil fuel consumption and global warming has been driving the worldwide revolution towards renewable energy. Biomass is abundant and low-cost resource whereas it requires environmentally friendly and cost-effective conversion technique. Pyrolysis of biomass into valuable bio-oil has attracted much attention in the past decades due to its feasibility and huge commercial outlook. However, the complex chemical compositions and high water content in bio-oil greatly hinder the large-scale application and commercialization. Therefore, catalytic pyrolysis of biomass for selective production of specific chemicals will stand out as a unique pathway. This review aims to improve the understanding for the process by illustrating the chemistry of non-catalytic and catalytic pyrolysis of biomass at the temperatures ranging from 400 to 650 °C. The focus is to introduce recent progress about producing value-added hydrocarbons, phenols, anhydrosugars, and nitrogen-containing compounds from catalytic pyrolysis of biomass over zeolites, metal oxides, etc. via different reaction pathways including cracking, Diels-Alder/aromatization, ketonization/aldol condensation, and ammoniation. The potential challenges and future directions for this technique are discussed in deep. Display omitted •Properties of lignocellulosic biomass and its pyrolysis chemistry are extensively reviewed.•Catalytic pyrolysis of lignocellulosic biomass for selective production of valuable chemicals is outlined.•Different catalytic reforming pathways are summarized.•Future research directions and technological challenges are proposed.