Modified sodium vermiculite, an iron-rich clay mineral, has been used in novel heterogeneous electrochemical Fenton-based treatments, so-called electro-Fenton (EF)-vermiculite, UVA photoelectro-Fenton (PEF)-vermiculite and solar photoelectro-Fenton (SPEF)-vermiculite. Tests were made with 130 mL of 0.150 mM Ponceau SS diazo dye in 0.050 M NaSO at pH 3.0, in the presence of 1.0 g L catalyst microparticles. The electrolyses were performed in an undivided cell with a boron-doped diamond anode (BDD) and air-diffusion cathode for HO production, at 33.3 mA cm. Decolorization and mineralization were upgraded in the sequence: EF-vermiculite < PEF-vermiculite < SPEF-vermiculite. The removal of organics occurred by the combined action of OH oxidant formed at the BDD surface and homogeneous and heterogeneous Fenton's reactions, along with the photolysis caused by UVA light or sunlight. The homogeneous Fenton's reaction resulted from iron ions leaching, but the heterogeneous mechanism was prevalent. Comparative treatments by anodic oxidation in the presence of HO and homogeneous EF were less effective than EF-vermiculite. The diazo dye absorbance decays agreed with a pseudo-first-order kinetics. SPEF-vermiculite was the most powerful process, yielding total decolorization and 84.1% mineralization after 300 and 360 min, respectively. The influence of catalyst concentration, current density and diazo dye content on PEF-vermiculite performance was examined. Oxalic, oxamic, malic, tartronic and acetic acids were detected as final short-linear carboxylic acids.