Biochar can effectively enhance the thermophilic anaerobic degradation of propionate. Nevertheless, previous studies frequently ascribed this enhancement to direct interspecies electron transfer (DIET) without considering the underlying kinetics and thermodynamics involved. Additionally, quantitative evaluation of biochar’s impact on interspecies electron transfer (IET) has been limited. In this study, we developed and optimized models for analyzing thermodynamics and electron transfer flux to elucidate the mechanism by which biochar enhances the two-step syntrophic methanogenesis of propionate. Findings revealed that biochar primarily facilitated DIET (1.78 × 10−4 A), leveraging its redox capacity. Additionally, it synergistically enhanced interspecies hydrogen transfer (4.08 × 10−10 A), significantly improving IET efficiency. This synergistic effect led to accelerated oxidative degradation rates of propionate (39.2 %) and intermediate acetate (13.5 %), expanding the thermodynamic windows for their syntrophic methanogenesis (221 % and 103 %, respectively). Accordingly, biochar increased the maximum rate of propionate methanation (71.9 %) and reduced the lag phase time (51.1 %). Moreover, biochar promoted the specific growth rates of acetogenic bacteria and methanogens while significantly increasing the abundance of Pelotomaculum, Methanoculleus, and Methanosarcina. These findings provide new insights and theoretical support for the use of biochar in promoting anaerobic digestion and facilitating IET during the process.