The present study reports the pervaporative separation capability of the pristine and polyhedral oligomeric silsesquioxanes (POSS) loaded hybrid polyether-block-amide (PEBA) membranes for n-butanol recovery from the dilute n-butanol-water mixtures. It is the first study to produce POSS-loaded PEBA membranes for n-butanol recovery. The morphology and crosslinking structure of the pristine and hybrid membrane were characterized by scanning electron microscopy and Fourier transform infrared spectroscopy. The thermal stability and crystallization behaviors of the pristine and hybrid membranes were investigated using thermogravimetric analysis and differential scanning calorimetry methods. Swelling experiments were also done to determine the affinity of the membranes to the n-butanol-water mixture. The effect of increasing amount of POSS on pervaporation performance was investigated in terms of flux and the n-butanol separation factor at 40 degrees C and a given n-butanol. All the hybrid membranes exhibited high flux and n-butanol separation factor than that of the pristine PEBA membrane. The best n-butanol separation factor of 27.2 was obtained accompanied with 1.33 Kg m(-2) h(-1) of flux, when the POSS amount was 4 wt %. (c) 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45211.