The present study is to investigate the reactivity of free radicals (SO4 center dot- and HO center dot) generated from common oxidants (peroxomonosulfate (PMS), peroxodisulfate (PDS) and hydrogen peroxide (HP)) activated by electrochemically generated Fe2+/Fe3+ ions which furthermore are evaluated to destroy pentachlorophenol (PCP) in aqueous solution. The effect of solution pH and amount of oxidants (PMS, PDS and HP) in electrocoagulation (EC) on PCP degradation is analyzed in detail. The experimental results reveal that, optimum initial solution pH is 4.5 and PMS is more efficient oxidant addition in EC. 75% PCP degradation is achieved at 60 min electrolysis time from PMS assisted EC. According to the first order rate constant, faster PCP degradation rate is obtained by PMS assisted EC. The PCP degradation rate by oxidant assisted EC is observed in the following order: EC/PMS > EC/PDS > EC/HP > EC. Further to identify the influences of experimental factors involved in PCP degradation by oxidant assisted EC, an experimental design based on an orthogonal array (OA) L-9 (3(3)) is proposed using Taguchi method. The factors that most significantly affect the process robustness are identified as A (oxidant) and B (pH) which together account for nearly 86% of the variance. (C) 2014 Elsevier B.V. All rights reserved.