Cu(II)-Fe(II)-H2O2 process was studied through degrading 3-nitroaniline (3-NA) in water under microwave (MW) irradiation. The experimental conditions were studied by investigating the removal rates and reaction rate constants of 3-NA at different levels of influence factors. The removal rates and reaction rate constants both increased with the increase of Cu(II), Fe(II) and H2O2 dosages when they were at reasonable concentration ranges ([Cu(II)] 0.0016-0.0094 mmol L-1, [Fe(II)] 0.051-0.205 mmol L-1 and [H2O2] 4.34-17.34 mmol L-1). Under the examined conditions (initial pH = 5.3, [Cu(II)], [Fe(II)] and [H2O2] were 0.0078, 0.205 and 17.37 mmol L-1, respectively, P-MW = 100 W, V3-NA = 400 mL), more than 92% of 3-NA was removed at 8.5 min and the reaction rate constant reached 0.310 min(-1). Furthermore, the mathematical relationship between reaction rate constants and reactants concentrations was obtained via kinetic study, the result was k = 43.9 . e(-2905.2/T) center dot [H2O2](1.675) center dot [Fe(II)](0.908) center dot [Cu(II)](0.080). Finally, the probable effect of Cu(II) in Cu(II)-Fenton process under MW irradiation was speculated according to the comparison result of 2-hydroxyterephtalic acid (generated by the reaction between hydroxyl radicals and terephthalic acid) intensity, the study of synergetic effects of Cu(II) and Fe(II) in Cu(II)-Fenton process and the comparative analysis of reaction mechanisms in Fenton process and Cu(II)-H2O2 process. (C) 2014 Elsevier B.V. All rights reserved.