Persulfates ((peroxymonosulfate (PMS) and peroxydisulfate (PDS)) can disintegrate waste activated sludge (WAS), but their influence on volatile fatty acid (VFA) production during anaerobic fermentation is largely unclear. Particularly, it is unknown whether persulfates can improve fermentation without any preactivation. This study investigated how the direct addition of PMS and PDS into the fermenter influences VFA production from WAS, and uncovered possible mechanisms of improved VFA production. At the PMS dosage of 1.0 mM/gVS, maximum VFA yield (1025 +/- 55 mg COD/L) was observed in 5 days of fermentation, which was 24% higher than that with an equimolar addition of PDS and 132% higher than that without persulfate addition. However, the cost-effectiveness of PMS in enhancing VFA production is lower than that of PDS. The in situ generated hydroxyl and sulfate radicals from persulfates in the fermenter enhanced not only WAS disintegration and solubilization but also the formation of biodegradable substances for acidification. Moreover, the direct addition of persulfates into the fermenter shifted the microbial community toward hydrolysisacidification such as Clostridium_sensu_stricto_10 and Fonticella. Results of this study also suggest that preactivation is not necessary when persulfates are applied to improve WAS fermentation.