The determination of strong oxidizing species is of outmost importance in a number of practical applications. However, the currently available analytical tools should be improved in terms of reliability, automation, and costs. With this respect amperometric techniques are particularly promising candidates; nevertheless, the performance of conventional electrode materials, such as Au and Pt, are unsatisfactory, particularly in terms of resistance to fouling. In addition, electroanalytical methods and devices most commonly pay highest attention to the determination of similar analytes present in trace. On the other hand, the determination of high concentrations is of particular importance in industrial and environmental frames. Especially with reference to similar situations, the present paper reports the electrochemical behavior and analytical effectiveness of an alternative electrode material, namely Cu, in the presence of H2O2 at high concentrations (up to 0.5 M) and at different pH values. Furthermore, the behavior in real, harsh matrices, namely wastewater samples exhibiting different levels of chemical oxygen demand, is also reported. The results have been fruitfully employed in the development of an analytical procedure for the determination of H2O2 in similar matrices. A statistical treatment of the electrochemical responses suggests that the repeatability and reproducibility are well adequate. (C) 2015 Elsevier Ltd. All rights reserved.