The separation of aromatic/aliphatic hydrocarbon mixtures is crucial in the petrochemical industry. Pervaporation is regarded as a promising approach for the separation of aromatic compounds from alkanes. Developing membrane materials with efficient separation performance is still the main task since the membrane should provide chemical stability, high permeation flux, and selectivity. In this study, the hyperbranched polymer (HBP) was deposited on the outer surface of a polyvinylidene fluoride (PVDF) hollow-fiber ultrafiltration membrane by a facile dip-coating method. The dip-coating rate, HBP concentration, and thermal cross-linking temperature were regulated to optimize the membrane structure. The obtained HBP/PVDF hollow-fiber-composite membrane had a good separation performance for aromatic/aliphatic hydrocarbon mixtures. For the 50%/50% (mass) toluene/n-heptane mixture, the permeation flux of optimized composite membranes could reach 1766 g center dot m-2 center dot h-1, with a separation factor of 4.1 at 60 degrees C. Therefore, the HBP/PVDF hollow-fiber-composite membrane has great application prospects in the pervaporation separation of aromatic/aliphatic hydrocarbon mixtures. (c) 2024 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All rights reserved.