a] 4-Aminoantipyrine (4-AA), a persistent metabolite of dipyrone found in natural water, has been treated in 100 mL of aqueous 0.050 M Na 2 SO 4 solutions at pH 3.0 by photoelectro-Fenton (PEF) with a 4 W UVA lamp. The assays were performed in a cell equipped with a boron-doped diamond (BDD) anode and an air-diffusion cathode for H 2 O 2 generation. The formation of an unstable Fe(III)-4-AA complex with 1 : 2 molar ratio was evidenced. A 2 4 central composite design was used to assess the effect of four independent variables on PEF performance.The optimized conditions for 62.5 mg L À 1 4-AA were: current density of 77.5 mA cm À 2 and 47.75 mg L À 1 Fe 2 + , yielding 99 % 4-AA degradation at 7 min, and 45 % 4-AA mineralization with 3.2 % mineralization current efficiency at 130 min. Slightly slower degradation and similar mineralization were obtained under these conditions when 4-AA was spiked into a municipal secondary effluent, showing a low influence of natural organic matter on PEF. The initially high acute toxicity determined using Artemia salina was largely diminished upon PEF treatment.