• A novel hyperbranched polymer (HBP) hollow-fiber composite membrane was fabricated via a facile dip-coating method on a PVDF ultrafiltration membrane.
• The optimized membrane achieved a high permeation flux of 1766 g·m⁻²·h⁻¹ and a separation factor of 4.1 for a 50/50 wt% toluene/n-heptane mixture at 60 °C.
• The study demonstrates the potential of HBP/PVDF hollow-fiber membranes for industrial pervaporation separation of aromatic/aliphatic hydrocarbons.
• The membrane offers advantages of self-supporting structure, high packing density, and ease of scale-up compared to flat-sheet and tubular modules.