Iron-based chemically enhanced primary sedimentation (CEPS) is increasingly adopted for wastewater treatment in mega cities, producing a large amount of sludge (Fe-sludge) with a high content of organics for potential organic resource recovery. In this experimental study, acidogenic fermentation was applied treat FeCl3-based CEPS sludge for production of volatile fatty acids (VFAs) at different pHs. Batch fermentation tests on the Fe-sludge with an organic content of 10 g-COD/L showed that the maximum VFAs production reached 2782.2 mg-COD/L in the reactor without pH control, and it reached 688.4, 3095.3, and 2603.7 mg-COD/L in reactors with pHs kept at 5.0, 6.0 and 8.0, respectively. Analysis of the acidogenesis kinetics and enzymatic activity indicated that the alkaline pH could accelerate the rate of organic hydrolysis but inhibited the further organic conversion to VFAs. In semi-continuous sludge fermentation tests, the VFAs yield in the pH6 reactor was 20% higher than that in the control reactor without pH regulation, while the VFAs yield in the pH8 reactor was 10% lower than the control. Illumina MiSeq sequencing revealed that key functional microorganisms known for effective sludge fermentation, including Bacteroidia and Erysipelotrichi, were enriched in the pH6 reactor with an enhanced VFAs production, while Clostridia became more abundant in the pH8 reactor to stand the unfavorable pH condition. The research presented acidogenic fermentation as an effective process for CEPS sludge treatment and organic resource recovery and provided the first insight into the related microbial community dynamics. Display omitted •Fe-based CEPS sludge was fermented at different pHs for production of VFAs.•Highest VFAs yield occurred in CEPS sludge fermentation at stable pH 6.•Microbial community dynamics was reported for the CEPS sludge acidogenesis.•100 mg-COD/L of organic was recovered from wastewater via CEPS sludge fermentation.