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The utilization of renewable lignocellulosic biomasses for bioenergy synthesis is believed to facilitate competitive commercialization and realize affordable clean energy sources in the future. Among the pathways for biomass pretreatment methods that enhance the efficiency of the whole biofuel production process, the combined microwave irradiation and physicochemical approach is found to provide many economic and environmental benefits. Several studies on microwave-based pretreatment technologies for biomass conversion have been conducted in recent years. Although some reviews are available, most did not comprehensively analyze microwave–physicochemical pretreatment techniques for biomass conversion. The study of these techniques is crucial for sustainable biofuel generation. Therefore, the biomass pretreatment process that combines the physicochemical method with microwave-assisted irradiation is reviewed in this paper. The effects of this pretreatment process on lignocellulosic structure and the ratio of achieved components were also discussed in detail. Pretreatment processes for biomass conversion were substantially affected by temperature, irradiation time, initial feedstock components, catalyst loading, and microwave power. Consequently, neoteric technologies utilizing high efficiency-based green and sustainable solutions should receive further focus. In addition, methodologies for quantifying and evaluating effects and relevant trade-offs should be develop to facilitate the take-off of the biofuel industry with clean and sustainable goals. • Fundamental and characteristic of microwave assisted pretreatment were introduced. • Effects of microwave irradiation on the lignocellulosic biomass reviewed. • Combination of microwave physicochemical methods obtained higher efficiency. • Energy and economic aspects of microwave-physicochemical methods evaluated. [ABSTRACT FROM AUTHOR]