Poly(ω-pentadecalactone-co-ε-caprolactone) copolymer (PDL-CL) is an enzymatically synthesized aliphatic biopolyester, which has been participated in a nanofibrous structure for the first time. Electrospinning of this synthetic polymer by blending with a natural polymer such as gelatin (Gel) could provide new characteristics that are significant for biomedical applications, such as drug delivery, wound healing, and tissue engineering. In the present study, PDL-CL/Gel nanofibrous membranes were successfully produced and characterized. The average diameter of nanofibers was 305.0 ± 45.5nm that may be beneficial in applications mentioned above. In order to increase hydrolytic resistance, cross-linking with glutaraldehyde vapor was applied. Cross-linking for 2h was enough to obtain a nanofibrous membrane that was able to resist in pH7.4 phosphate buffered saline for 30 days. In addition, contact angle measurement results had shown that, cross-linked nanofibrous membrane had good wettability, which is a required specification to be applied in biomedical field. Hence, this study provides an overview on fabrication of fine PDL-CL/Gel nanofibers, which may have potential to be used in biomedical area.