Microwave (MW) heating has gained significant attention in food industries and biomass-to-biofuels through pyrolysis over conventional heating. However, constraints for promoting MW heating related to the use of different MW absorbers are still a major concern that needs to be investigated. The present study was conducted to explore the MW heating performance of biochar as a low-cost MW absorber for performing pyrolysis. Experiments were performed on biochar under different biochar dosing (25 g, 37.5 g, 50 g), MW power (400 W, 700 W, 1000 W), and particle sizes (6 mm, 8 mm, 10 mm). Results showed that MW power and biochar dosing significantly impacted average heating rate (AHR) from 17.5 to 65.4 °C/min at 400 W and 1000 W at 50 g. AHR first increased, and then no significant changes were obtained, from 37.5 to 50 g. AHR was examined by full factorial design, with 94.6% fitting actual data with predicted data. The model suggested that the particle size of biochar influenced less on AHR. Furthermore, microwave absorption efficiency and biochar weight loss were investigated, and microwave absorption efficiency decreased as MW power increased, which means 17.16% of microwave absorption efficiency was achieved at 400 W rather than 700 W and 1000 W. Biochar weight loss estimated by employing mass-balance analysis, 2–10.4% change in biochar weight loss was obtained owing to higher heating rates at higher powers and biochar dosing.