The removal of high-concentration C.I. acid orange 7 (AO7) in aqueous solution by the prepared iron/copper (Fe/Cu) bimetallic particles and zerovalent iron (ZVI) was investigated thoroughly. Fe/Cu bimetallic particles were prepared by planting Cu on the surface of Fe. Experimental results confirmed the superiority of Fe/Cu bimetallic particles for the degradation of AO7 in aqueous solution. Under the optimal conditions ([Fe/Cu](0) = 40 g.L-1, [AO7](0) = 1000 mmol.L-1, initial pH = 6.5, TMLCu = 0.62 g of Cu/g of Fe), the AO7 concentration and chemical oxygen demand (COD) and total organic carbon (TOC) removal efficiencies could reach 94.3%, 61.8%, and 60.8%, respectively, after only 10 min of treatment by Fe/Cu bimetallic particles. Under the same conditions, however, the AO7 concentration and COD and TOC removal efficiencies by ZVI only reached 35.5%, 25.1%, and 21.2%, respectively. Thus, the planting of Cu could improve the reactivity of Fe. The degradation of AO7 was analyzed by UV-vis and Fourier transform infrared spectra, and the results show that the chromophore part (i.e., -N=N-) of AO7 could be destructed by Fe/Cu bimetallic particles. Additionally, its degradation products might be sulfanilamide and 1-amino-2-naphtol, which would be removed by further mineralization of Fe/Cu bimetallic particles or sedimentation of Fe ions. Therefore, the Fe/Cu bimetallic system is a promising process for the toxic and refractory wastewater from the printing and dyeing industry.