This work aims to evaluate the feasibility of using imidazolium ionic liquids (ILs) in the design of multiphase bioreactors for the removal of volatile organic compounds (VOCs). The IL affinity for three model VOCs (dimethyl sulfide, dimethyl disulfide and toluene) was evaluated by means of the dimensionless partition coefficient (K). It was observed that ILs showed K values comparable to typical liquid solvents used in multiphase bioreactors for VOC biodegradation (K values ranged from 0.009 to 0.011, 0.0012 to 0.0013 and 0.00061 to 0.00096 for dimethyl sulfide, dimethyl disulfide and toluene, respectively). Toxicity tests showed that both ILs at concentrations of 5% and 10% (v/v) inhibited the glucose uptake of an activated sludge during approximately 24 h. After such lag period, the microorganisms were able to recover its metabolic activity. However, VOC biodegradation experiments showed that ILs at 5% (v/v) were toxic for the activated sludge and a toxic synergistic effect of the IL-VOC combination likely occurred. After acclimation to the target VOCs, only the toluene biodegradation capacity was significantly increased in the presence of ILs. These toxic effects represent a key drawback for the potential of IL-based multiphase systems devoted to VOC biodegradation. Therefore, this study suggests that microbial acclimation only to the VOCs is not enough to get an efficient biodegradation in multiphase systems including ILs as non-aqueous phases. (C) 2011 Elsevier Ltd. All rights reserved.