Peroxodiphosphate can be produced efficiently by electrolyses of phosphate solutions with boron-doped diamond electrodes. This oxidant is proposed in literature as a promising alternative to persulphates and to other oxidants typically used in environmental remediation processes and it is also known to have a significant role in the Understanding Of the electrolyses of wastes polluted with organics when phosphates are contained in significant concentrations in the waste. This manuscript clarifies the reactivity of solutions containing electrochemically produced peroxophosphate solutions with various aromatic (phenol and naphthol) and aliphatic (maleic acid and 2-propanol) organic pollutants and also with cyanide, and compares results obtained in these chemical oxidation test with those obtained using similar oxidants such as hydrogen peroxide, peroxosulphate and hypochlorite. Results show that peroxodiphosphate can oxidize organic pollutants but it is much less powerful than hydrogen peroxide. Opposite, the oxidation of cyanide with this oxidant seems to offer significant advantages if compared with that of hypochlorite and shows a very promising process to treat efficiently wastes polluted with cyanide. In every case, it was demonstrated that oxidation efficiency of peroxophosphate produced electrochemically is much more significant than that shown by commercial peroxosulphate. (C) 2013 Elsevier B.V. All rights reserved.