AbstractPoly(butylene succinate) (PBS) and poly(butylene/2‐butyl,2‐ethyl‐propylene succinate) (PBSBEPS) membranes are prepared by electrospinning technique. In recent years, interest in biodegradable aliphatic polyesters, including PBS and its copolymers, is increasing as they have potential applications in various sectors such as mulching films, food packaging, tissue engineering, and drug delivery. In this work, the synthesized polymers are dissolved in different solvents, namely acetone, chloroform (CHCl3), methanol, dichloromethane (DCM), and dimethylformamide in order to obtain the best solvent system. These solutions are then electrospun at room temperature to produce micron‐sized fibers. The variables examined in determining the optimal solution and electrospinning conditions are the solvent system used, the concentration of PBS and PBS‐based random copolymer, applied voltage, flow rate, humidity, and the distance between the needle tip and the collector, all of which have a meaningful effect on the fiber morphology. Among the various solvents used, the DCM and the less toxic CHCl3 result in fewer bead defects among fibers. Besides, an increase in PBS and PBS‐based random copolymer concentration determines the reduction of bead defects, which from 12 to 14 wt% results in bead‐free uniform fibers, when suitable processing parameters are set. Promising results, which can pave the way for the production of membranes loaded with appropriate anticancer molecules for targeted biomedical applications, are obtained.