Capturing the carbon in volatile fatty acids (VFA) produced from the anaerobic digestion (AD) of sewage sludge has the potential to not only provide economic benefits but also reduce greenhouse gas production. This study demonstrates a chemical–free method to collect VFA from an AD instead of methane that involves electrochemical pretreatment (EPT) of sludge. Experimental results show that applying 15 V EPT for 45 min enhances acidogenesis and selectively inhibits methanogenesis, leading to a substantial VFA accumulation (2563.1 ± 307.9 mg COD/L) and achieving 2.5 times more carbon fixation than via methane production. Interfacial thermodynamic analysis shows that EPT induces a decrease in both the repulsive electrostatic energy (from 152.9 kT to 12.2 kT) and the energy barrier (from 57.0 kT to 2.6 kT) in the sludge, leading to increased sludge aggregation and entrapment of microorganisms. Molecular docking sheds lights on how the methanogens interacts with the organic matter released from EPT (e.g., alanine–tRNA ligase), showing that these interactions potentially interfere with the proteins that are associated with the activities of the methanogens and the electron transfer pathways, thereby impeding methanogenesis. Integrating EPT into AD therefore facilitates the recovery of valuable VFA and the capture of carbon from freshwater sludge, providing notable economic and environmental benefits in sewage sludge treatment.