para-Chloronitrobenzene (p-CNB) is particularly harmful and persistent in the environment and is one of the priority pollutants. A feasible degradation pathway for p-CNB is bioreduction under anaerobic conditions. Bioreduction of p-CNB using a hydrogen-based hollow fiber membrane biofilm reactor (HFMBfR) was investigated in the present study. The experiment results revealed that p-CNB was firstly reduced to para-chloraniline (p-CAN) as an intermediate and then reduced to aniline that involves nitro reduction and reductive dechlorination with H(2) as the electron donor. The HFMBfR had reduced p-CNB to a major extent with a maximum removal percentage of 99.3% at an influent p-CNB concentration of 2 mg/L and a hydraulic residence time of 4.8h, which corresponded to a p-CNB flux of 0.058 g/m(2) d. The H(2) availability, p-CNB loading, and the presence of competing electron acceptors affected the p-CNB reduction. Flux analysis indicated that the reduction of p-CNB and p-CAN could consume fewer electrons than that of nitrate and sulfate. The HFMBfR had high average hydrogen utilization efficiencies at different steady states in this experiment, with a maximum efficiency at 98.2%. (C) 2011 Elsevier B.V. All rights reserved.