The field of nanofiber research has been gradually shifting towards sustainable materials, but the main challenges include modifying their properties to fit specific needs and applications. In this study, ultrathin and porous biobased poly(butylene succinate) (PBS) membranes were fabricated using electrospinning. The neat PBS polymer was found to be very difficult to process, but defect-free nanofibers were generated by adding cetyltrimethylammonium bromide (CTAB) as a surfactant. To determine the effect of CTAB on PBS membranes, extensive characterization of the newly developed material was performed, including morphology, wettability, water absorption, thermal, mechanical, and hydrolytic degradation properties. Scanning electron microscopy (SEM) showed that adding 0.04% w/v of CTAB produced smooth and beadless nanofibers with an average diameter of 380 nm. The presence of CTAB, as a surfactant, significantly improved the membrane porosity and generated higher hydrophilicity even when starting with an intrinsically hydrophobic material (original PBS). The result was a higher water absorption and hydrolytic degradation of the membrane. On the mechanical side, the surfactant highly improved the elongation at break from 51% for the neat PBS membrane to 192% for the PBS/CTAB membrane with 0.04% w/v CTAB. However, CTAB addition had a negligible effect on thermal stability and crystallinity. The results of this study showed that the high porosity and hydrophilicity of PBS/CTAB electrospun membranes, combined with their outstanding water absorption capacity, elasticity, and biodegradability, present a novel solution for enhancing the performance and functionality of biomaterials in various biomedical fields, especially in tissue engineering and wound dressing applications. Display omitted •Polybutylene succinate (PBS) nanofibers were generated via solution electrospinning.•CTAB (surfactant) was needed to generate stable nanofibers.•Membranes with good wettability and excellent water absorbance were produced by combining PBS and CTAB.•Faster hydrolytic degradation was observed due to CTAB.