Chlorophenol degradation was achieved using a combination of hydrodechlorination and heterogeneous Fenton-like oxidation. The process was conducted at ambient conditions (25 +/- 2 degrees C, atmospheric pressure) as a one-pot reaction involving formic acid as H-2 source for both hydrodechlorination of chlorophenols and H2O2 formation. An alumina-supported Pd-Fe catalyst was applied, which is able to decompose formic acid at the Pd sites, forming H-2 and CO2, and additionally H2O2 in the presence of O-2. At the same time, due to presence of iron sites on the catalyst, the H2O2 formed can be utilized for a Fenton-like oxidation reaction. Three different reaction protocols were tested, including: (i) consecutive reduction-oxidation with an initial oxygen-free phase adjusted by He purging (CRO-He), (ii) consecutive reduction-oxidation with initially oxygen-limited conditions (CRO) and (iii) simultaneous reduction-oxidation where O-2 flowing was started at the beginning of the reaction (SRO). 2,4-Dichlorophenol (DCP) and pentachlorophenol (PCP) were selected as representatives for the group of chlorophenols. For DCP degradation, CRO-He and SRO showed similar efficiencies with respect to the mineralization degree (up to 70%), whereas SRO achieved a better detoxification as observed in bioluminescence tests. The CRO-He reaction over the catalyst used showed only a small decrease in its activity during the oxidation stage, with no further change after the catalyst had been recovered twice. For PCP degradation, a self-inhibition effect was observed for the SRO process, indicating that PCP is hardly degradable by catalytic oxidation. In this case, the CRO-He process, which was facilitated by initial transformation of PCP into phenol and its subsequent oxidation, clearly produced a cleaner medium. This was also confirmed by the results of the toxicity measurements. The catalyst indicated a promising stability based upon the Pd and Fe leaching results measured at the end of each run. (C) 2011 Elsevier B.V. All rights reserved.