Phosphorus release and sludge hydrolysis are the keys for phosphorus and carbon recovery from sewage sludge via anaerobic process. In this study, iron-rich sludge (a common phosphorus-rich sewage sludge) was pre-oxidized by heat-activated peroxydisulfate (PDS) to enhance volatile fatty acids (VFAs) production and iron-bound phosphorus (Fe-P) release during anaerobic fermentation (AF). With low-dosage PDS pre-oxidation (33.75 mg/g total solids), the concentration of recoverable phosphorus increased by 49.3% than those noted in control along with enhanced VFAs production after 4 days. This is mainly because PDS oxidation not only effectively disintegrated sludge, but also generated sulfate simultaneously. Sludge disintegration enhanced organic matter hydrolysis, promoting VFAs yield, while sulfate was reduced to sulfide during AF and precipitated with iron, leading to Fe-P release. The application of PDS pre-oxidation on iron-rich sludge could not only improve the resourcefulness of sludge but also reduce secondary pollution (sulfate or hydrogen sulfide).