In this study, the degradation of the ionic liquid (IL) 1,3-dicyclohexylbenzimidazolium chloride ([DCy6bim][Cl]) was carried out by applying an heterogeneous electro-Fenton (HEF) treatment using iron alginate spheres (FeAS) as catalyst. Initial trials were performed at current between 50 and 250mA, different FeAS dosages (1-5g), and [DCy6bim][Cl] concentrations (70-280mgL(-1)) as key parameters for the characterization of the HEF process. Comparative experiments suggest that high current, low FeAS dosage and low [DCy6bim][Cl] concentration are the best conditions to yield near complete total organic carbon decay after 4h. In order to evaluate the catalyst behaviour and iron leaching during the degradation of [DCy6bim][Cl], differential pulse voltammetry (DPV), a sensitive and selective electroanalytical technique, was used to monitor the IL degradation, by-products and iron evolution into the solution at high concentration levels. The profile of the voltammetric curves obtained by DPV suggests almost complete cleavage of the cation structure of [DCy6bim][Cl] during the first 120min. At longer treatment times, DPV revealed the generation of iron complex with chloride and carboxylic acids. Finally, chromatographic analysis of these carboxylic acids and inorganic anions permitted to validate the results obtained by DPV and demonstrated the feasibility of the HEF process for IL degradation. [GRAPHICS] .