Due to its toxicity to ecosystem, phenol removal from industrial wastewater before discharge is a priority concern. Extractive membrane bioreactor (EMBR), a novel wastewater treatment process combining aqueous-aqueous extractive membrane process and biodegradation, has shown potential in treating phenol in wastewater. In this paper, composite hollow fiber membranes with different levels of poly (dimethylsiloxane) (PDMS) intrusion were prepared by coating a layer of PDMS on a Polyetherimide (PEI) hollow fiber substrate. Their applicability to EMBR for phenol removal was studied. The prepared membranes were characterized by microscopy and gas permeation test, and their performances were evaluated in aqueous-aqueous extractive membrane processes and EMBR process. The overall mass transfer coefficient for phenol, or k(0), was found to be significantly affected by the level of PDMS intrusion in the composite membranes. This is because the penetration of PDMS into the porous substrate results in a denser membrane structure, which consequently increases the membrane resistance. A slight penetration of PDMS into the substrate was found to be necessary for the composite membranes to achieve high k(0) while maintaining low inorganic flux across the membranes. Wilson-plot analysis suggests that membrane resistance dominated over liquid boundary layer resistances. After more than 250 h of EMBR operation, significant biofilm growth was observed on the composite membranes and the k(0) was dropped but stabilized at around 7.5 x 10(-7) m/s. This k(0) was 7.5 times higher than commercial PDMS tubular membranes (without biofilm development) reported in previous studies, confirming the superiority of thin film composite membranes prepared in this work. It was also found that process optimization to control biofilm thickness is important in order to enhance phenol removal rate in EMBR. (C) 2015 Elsevier B.V. All rights reserved.