Phosphorus (P) in nature mostly exists in an insoluble state, and humic reducing microorganisms (HRMs) can dissolve insoluble substances through redox properties. This study aimed to investigate the correlations between insoluble P and dominant HRMs amenable to individual culture during biochar composting. These analyses revealed that, in comparison to the control, biochar addition increased the relative abundance of dominant HRMs by 20.3% and decreased redox potential (Eh) levels by 15.4% hence, enhancing the moderately-labile-P and nonlabile-P dissolution. The pathways underlying the observed effects were additionally assessed through structural equation modeling, revealing that biochar addition promoted insoluble P dissolution through both the direct effects of bacterial community structure as well as the direct effects of HRMs community structure and indirect effects based on Eh of HRMs community structure. This research offers a better understanding of the effect of HRMs on insoluble P during the composting process.