A hollow fiber-supported liquid membrane (HFSLM) configuration with a large membrane surface area per volume is becoming more viable and feasible to use on an industrial scale. However, the hollow fiber (HF) forms a thicker skin outer layer than its flat-sheet equivalents, resulting in lower membrane fluxes and more unsatisfactory performance. Therefore, this study investigated the effect of HF spinning parameters such as bore liquid type, air gap distance (3–12 cm), and air relative humidity (64–100 wt%) on the properties and performance of HFSLM for levulinic acid (LA) extraction. The HF membranes were characterized in terms of morphology, contact angle, porosity, and membrane tensile strength. Polyethersulfone-based HF membrane prepared using 60% v/v dimethylacetamide as bore liquid at 6 cm air gap distance and 86% air relative humidity resulted in the highest LA extraction of 72.2%. The membrane had a dual symmetric finger-like structure with an open porous structure. The value of the outer fiber surface contact angle, porosity, and tensile stress was 94.1°, 77.57%, and 1,524.7 kPa, respectively. An optimal spinning condition is crucial in producing the best HF structure for improving the HFSLM performance in LA extraction.