We in this study investigated a novel electrochemical approach combining electro-enzyme and electrocoagulation to precipitate bisphenol A (BPA) from water containing humic acid (HA). Horseradish peroxidase was immobilized on the graphite felt of Ti electrode as HRP-GF/Ti cathode, with aluminum plate anode establishing a pair of working electrodes. BPA was 100% removed and the reduction of total organic carbon (TOC) reached 95.1% after 20-min sequencing treatment with the current density of 2.3 mA/cm(2). Real wastewater (TOC= 28.76 mg/L, BPA =4.1 mu g/L) also can achieve 94% BPA removal and 52% TOC reduction after sequencing treatment. Additionally, coupled electro-system with continuous flow only required energy of 0.016 kWh/m(3) to achieve simultaneous 90% BPA and 85% TOC removal. As indicated in the time-of-flight mass spectrometry and FTIR spectra, the electro-enzymatic process not only oxidized BPA into dimer and BPA-3,4-quinone, but also greatly altered the chemical and structural features of HA, where hydrophilic moieties (phenolic and alcohols) transformed into hydrophobic forms (ethers, quinone and aliphatic). These polymerized products were effectively separated from aquous solution during anodic electrocoagulation, leading to significant removal of BPA and TOC. Thus, the coupled process may provide a faster and less energy strategy to control certain emerging contaminants in water/wastewater treatment. (C) 2015 Elsevier B.V. All rights reserved.