Peroxydisulfate (PDS) additive has been proven as an effective strategy to enhance short-chain fatty acids (SCFAs) production from waste activated sludge (WAS), which can achieve dual objectives of waste disposal and resource recovery. However, the high cost of PDS limits its large-scale application in sludge treatment. This study explored the feasibility of using natural pyrite (FeS2) as an activator for PDS to enhance its capacity for promoting SCFAs production while reducing the required dosage. Compared to sole PDS (1 mM/g volatile suspended solids (VSS)), FeS2/PDS co-treatment (0.5 mM/g VSS PDS + 0.6 mM/g VSS FeS2) obviously increased the maximum SCFAs production from 4589.5 mg COD/L to 5951.3 mg COD/L, accompanied with an enhanced proportion of acetate from 62.0 % to 75.2 %. Mechanism exploration revealed that FeS2/PDS enhanced the generation of hydroxyl radicals (•OH) and sulfate radicals (SO4•−), thereby promoting WAS solubilization and hydrolysis. The detectable soluble chemical oxygen demand within the supernatant after 4 days of co-treatment fermentation was 5.3-fold higher than that in the single FeS2 test and 2.0-fold higher than that in the single PDS test. Meanwhile, the activities of key enzymes, including protease, α-glucosidase, acetate kinase, and butyrate kinase, were also significantly enhanced after the FeS2/PDS treatment, accompanied with an increase in the abundance of hydrolytic and acidogenic microorganisms such as Acinetobacter, Clostridium_sensu_stricto, and Fonticella. Besides, FeS2/PDS co-treatment improved the dewaterability (42.7 % reduction in capillary suction time) and reduced operation cost (37.9 % decrease), as compared to the sole PDS (1 mM/g VSS) treatment. These findings suggest that FeS2/PDS co-treatment is a promising and cost-effective technique to enhance WAS anaerobic fermentation.