With the increasing depletion of fossil resources and the growing serious environmental pollution, the development and utilization of environmentally friendly renewable resources have drawn widespread attention. Microwave pyrolysis of lignocellulosic biomass offers advantages such as fast reaction rates, easy control, and pollution-free operation. However, issues such as uneven product distribution and low economic value severe restrict the comprehensive and efficient utilization of biomass energy. This review systematically introduces the structure of lignocellulosic components, elaborates on the pyrolysis mechanisms of each component, compares the differences between microwave pyrolysis and traditional pyrolysis, discusses the influencing factors of microwave pyrolysis, and examines the product distribution of microwave-catalyzed pyrolysis of lignocellulosic biomass. Furthermore, various catalysts (carbon-based materials, molecular sieves, metal oxides, etc.) that promote microwave pyrolysis of biomass are introduced. These catalysts efficiently convert lignocellulosic biomass, optimize the distribution of microwave pyrolysis products, and facilitate the selective production of specific high-value chemicals, thereby promoting the resource utilization and value-added utilization of lignocellul osic biomass. Finally, the review presents prospects for future research directions and technological developments in lignocellulosic pyrolysis.