This study aimed to investigate the simultaneous removal of methylene blue (MB) and total dissolved copper (TCu) by heterogeneous zero-valent iron (ZVI) Fenton-like system (ZVI/H2O2) and elucidate the mechanism of synergistic effect for co-contaminants removal. Hydroxyl radical ((OH)-O-center dot) formation was hypothesized to be the dominant pathway for the oxidation of MB, confirmed by the quenching experiments and ESR analysis. And the synergistic effect of TCu and ZVI greatly promoted the release of Fe2+, further accelerating the generation of hydroxyl radical ((OH)-O-center dot) via Fenton reaction. The generation process of (OH)-O-center dot was unveiled by quenching experiments and electron spin resonance (ESR) analysis, while the processes of ZVI corrosion and TCu reduction were revealed through several characterization approaches including SEM, XRD, FTIR and XPS. The degradation pathway of MB was also investigated by LC-MS analysis. The MB initial concentration, TCu initial concentration, H2O2 dosage, ZVI dosage and initial solution pH could play crucial roles in the removal of MB and TCu. The influence of water matrix including inorganic anions (Cl-, NO3-, HCO3-) and actual water was finally conducted to elucidate the role of natural organic matter (NOM) in the environmental systems. (C) 2019 Elsevier Inc. All rights reserved.