Advanced oxidation processes (AOPs) based on the bimetallic system has been demonstrated as a promising way to enhance the degradation of pollutants in the water. In this study, the degradation of Rhodamine B (RhB) in a zero-valent iron (ZVI)/ peroxymonosulfate system with Cu²⁺ was thoroughly investigated. RhB could be efficiently removed (99.3 %) in the optimal ZVI/PMS/Cu²⁺ system, while only 58.2 % of RhB could be degraded in the ZVI/PMS system. The influence of reaction parameters on the degradation of RhB was further investigated. Quenching experiments and electron paramagnetic resonance (EPR) tests revealed that various reactive oxygen species could be generated in the ternary system, of which, ¹O₂ and O₂^{radical dot−} were identified for the first time. The effect of various anions, NOM and different water matrix were also considered at different concentrations. A variety of byproducts and degradation pathways were identified using HPLC/MS/MS. Finally, the Quantitative Structure Activity Relationship (QSAR) method of Toxicity Estimation Software Tool (TEST) was applied to estimate the toxicity of the byproducts and the results indicated that the overall toxicity of the target was relatively reduced. This study demonstrated the potential for the removal of environmental reluctant pollutants in water via the combined radical and non-radical pathways.