Tetrabromobisphenol A (TBBPA), a toxic persistent pollutant, should be effectively removed from the environment. In this study, an electrochemical sequential reduction-oxidation system was proposed by controlling reaction atmosphere with Pd-Fe nanoparticles modified Ni foam (Pd-Fe/Ni) electrode as cathode for TBBPA degradation. To obtain an efficient Pd-Fe/Ni electrode for TBBPA degradation, various factors, like Pd loading, Fe2+ adding amounts, were examined. The Pd-Fe/Ni electrode exhibited higher TBBPA conversion and debromination than the counterparts, due to the synergism of Fe-0 and electrochemical reduction. Similar TBBPA conversions and debromination ratios were observed for the cases of sparging N-2 only and sparging N-2 followed by air, which were higher than those of aeration. Reductive debromination occurred while first bubbling N-2, forming tri-BBPA, di-BBPA, mono-BBPA and BPA; and these intermediates were likely to be further oxidized by center dot OH generated from H2O2 together with Pd-Fe/Ni electrode under aeration. Reductive and oxidative intermediates (including aromatic ring-opened product) were identified by HPLC and UPLC-QTOF-MS. Based on the intermediates, the possible TBBPA degradation mechanism and pathway were proposed. This study demonstrates that sequential reduction oxidation process tuned by N2 and air bubbling was favored for TBBPA degradation, thus, it should be a promising process for HOCs degradation. (C) 2017 Elsevier B.V. All rights reserved.