Pervaporation could be a cost competitive process for separating aromatic/aliphatic hydrocarbon mixtures in the chemical industry. In this study, commercial poly(ether-block-amide) (PEBA) and ceramic tubular substrates were used to prepare pervaporation membrane for separating aromatic/aliphatic mixtures through a facile thermal crosslinking method. The adsorption and diffusion properties of toluene and n-heptane in PEBA were determined by swelling experiment and inverse gas chromatography technique. FIR and XRD were used to investigate the hydrogen bonding and crystallinity of PEBA molecule through thermal crosslinking. The morphology and structure of PEBA/ceramic composite membrane were characterized by SEM and EDX. The separation performance of the composite membrane can be adjusted by controlling PEBA concentration, thermal crosslinking temperature and time Ceramic tubular substrate could suppress the excessive swelling and thereby enhance the stability of the membrane. Furthermore, different types of fillers were incorporated into PEBA matrix to improve the separation performance. The results demonstrate that PEBA/graphite hybrid membrane has the highest separation factor for separating 50 wt% tolueneln-heptane mixtures. This study is expected to extend the membrane material and simplify the membrane preparation procedures in aromatic/aliphatic pervaporation fields. (C) 2015 Elsevier B.V. All rights reserved.