The degradation characteristics and pathways of pentachlorophenol (PCP) by the photo-fenton systems were studied in H2O2 aqueous solutions, which contained Fe(III) only [H2O2/Fe(lll) system] and Fe(lll) + humic acid (HA) [H2O2/Fe(lll)/HA system] at pH 5.0. Although 40% of the PCP was degraded after 5 h of irradiation in the H2O2/Fe(lll) system, more than 90% was degraded in the H2O2/Fe(lll)/HA system. This shows that at pH 5.0 the degradation of PCP is clearly enhanced by the presence of HA in the photo-Fenton system. In the H2O2/Fe(l II) system, the production of octachlorodibenzo-p-dioxin (OCDD) was detected, and 2-hydroxy nonachlorodiphenyl ether was also identified as a precursor of OCDD. However, no OCDD production was observed in the H2O2/Fe(lll)/HA system. This indicates that the presence of HA represses the production of OCDD during the degradation of PCP by the photo-fenton system. Such an effect by HA can be attributed to a reaction sequence wherein reaction intermediates derived from PCP, such as PCP., are incorporated into HA. This was verified by C-13 NMR and pyrolysis-GC/MS studies.