To obtain high-quality VFAs production from primary sludge, a novel strategy that combined peroxymonosulfate (PMS) pretreatment and alkaline fermentation (i.e., PMS & pH9) was proposed in the study. The results showed that PMS & pH9 was efficient in sludge solubilization and hydrolysis, resulting in a maximal VFAs yield of 401.2 mg COD/g VSS, which was 7.3-, 2.1-, and 8.8-fold higher than the sole PMS, sole pH9, and control, respectively. Acetate comprised 87.6% of VFAs in this integration system. Mechanism investigations revealed that sulfate and free radicals produced by PMS play roles in improving VFAs yield under alkaline conditions. Besides, sulfate also aided in C3∼C5 VFAs converting to acetate under alkaline conditions depending on the increase of incomplete-oxidative sulfate-reducing bacteria (iso-SRB) (i.e., Desulfobulbus and Desulfobotulus). Moreover, the relative abundances of acid-forming characteristic genera (i.e., Proteiniborus, Proteinilcasticum, and Acetoanaerobium) were higher in PMS & pH9.