Phosphorus is enriched in waste activated sludge (WAS) during wastewater treatment, and organic phosphorus (OP) is a potential slow-release P fertilizer. The chemical coagulants used in sludge dewatering leave numerous residues in WAS that affect sludge composting. In this study, the effects of polyaluminum chloride (PAC) and polyferric sulfate (PFS) on the bioconversion of dissolved OP (DOP) during sludge composting were investigated. The results revealed that PFS conditioning promoted the transformation and bioavailability of DOP, whereas PAC conditioning inhibited. Results indicated that PFS conditioning enhanced the transformation of OP molecules in the thermophilic phase. Through oxidation and dehydrogenation reactions, 1-hydroxy-pentane-3,4-diol-5-phosphate and D-ribofuranose 5-phosphate with high bioactivity were generated in the PFS-conditioned compost. Enzymatic hydrolysis experiments further verified that PFS conditioning enhanced the DOP bioavailability in the compost, whereas PAC conditioning inhibited it. The study has provided molecular insights into the effects of chemical conditioning on DOP conversion during sludge composting.