The recent development of microwave radiation technology has increased the application possibilities of waste tobacco stems (WTSs). In this study, the morphology and microwave absorption properties of tobacco stem materials as well as the pyrolysis of the resultant biomass (BMTS) were studied via thermogravimetry–differential scanning calorimetry (TG-DSC), scanning electron microscopy (SEM), mercury intrusion porosimetry (MIP), and a vector network analysis (VNA). The results show that the BMTS pyrolysis involves four stages in air: dehydration, heat transfer, pyrolysis, and carbonisation, and it involves three stages in N 2 : moisture evaporation, de-volatilization, and charring. The microwave-assisted expansion of WTSs can improve the pore diameter and total porosity of the expanded tobacco stems (ETSs) and BMTS. The latter is a macroporous material with a total porosity of 78.2% and a probable pore size of 29.5 μm. Its pore size distribution ranges from 10.7 nm to 227 μm. The microwave absorption properties of the WTSs are affected by the moisture content, bulk density, and grain size; the properties can be enhanced by decreasing the grain size and increasing the moisture content and bulk density within the experimental range. The 3 dB bandwidth and amplitude vary by 0.45 MHz and − 0.406 dB per 1% increase in the moisture content of the materials, respectively. Our results demonstrate that tobacco stem materials with different moisture contents and grain sizes should be classified before the expansion or re-drying steps to ensure heating uniformity and product quality during the microwave radiation treatment. Unlabelled Image • A new access to utilizing waste tobacco stem via microwave radiation was explored. • Morphology properties were comparatively investigated for microwave treated tobacco stem. • A macroporous material with higher porosity was prepared by microwave radiation. • Microwave-absorption properties were affected by the moisture content, bulk density and grain size. [ABSTRACT FROM AUTHOR]