This study presents the degradation of phenol by the photoelectro-Fenton method using nano zero-valent iron (nZVI) immobilized in polyvinyl alcohol-alginate beads. The effect of nZVI loading, H2O2 concentration, pH, and initial phenol concentration on phenol degradation and chemical oxygen demand reduction was studied. The scanning electron microscope images of the nZVI beads were used to analyze their morphology, and their diameters were in the range of 500-600 μm. The concentration of nZVI in the beads was varied from 0. 1 to 0. 6 g/L. Fe2+ leakage of 1 and 3 % was observed with 0. 5 and 0. 6 g/L of nZVI, respectively, and the observed beads' fracture frequency was 2 %, which confirmed the stability of the beads. The optimum operating conditions that arrived for better degradation were 0. 5 g/L of nZVI, pH 6. 2, and 400 mg H2O2/L. The treatment of effluent by this method increased the biodegradability index of the effluent, and the degradation data were found to follow pseudo first-order kinetics. © 2012 Springer-Verlag.