This study reports the feasibility of removing pentachlorophenol (PCP) by an acidogenic process in batch reactors. When the acidogenic sludge was first acclimated with 2,4,6-trichlorophenol (2,4,6-TCP) and developed 2,4,6-TCP dechlorinating activity, PCP could be ortho-dechlorinated to 3,4,5,-trichlorophenol (3,4,5-TCP) via 2,3,4,5-tetrachlorophenol as the intermediary. However, due to PCP's higher hydrophobicity and its higher expected Gibbs free energy yield, it was adsorbed to the sludge and dechlorinated preferentially to 2,4,6-TCP. This resulted in the inhibition of 2,4,6-TCP dechlorination. PCP removal under acidogenic condition was attributed to both reductive dechlorination and adsorption. At low PCP loads of 0.48 mu moles/g MLVSS.d, dechlorination was the dominant removal mechanism (69% of total removal), while at the higher PCP load of 9.3 mu moles/g MLVSS.d, adsorption was the main mechanism (82% of total removal). Attempts to induce meta or para position dechlorination of PCP failed when using meta position chlorophenols such as 2,3,6-TCP, 3,4,5-TCP and 3,5-DCP as the initial substrates. Overall, acidogenic biotreatment was an effective process in reducing PCP loads prior to downstream biological treatment. (C) 2008 Elsevier Ltd. All rights reserved.