Electrospinning of biodegradable poly(omega-pentadecalactone) (PPDL) is poorly investigated. In the present work, PPDL homopolymers of different molecular weight were synthesized by ring-opening polymerization of omega PDL, and then electrospun. Mixtures of PPDL with hexafluoro-2-propanol (HFIP) and with HFIP-chloroform blend were used for electrospinning. Since PPDL is poorly soluble in HFIP at high concentrations, the PPDL-HFIP mixture was turbid and its electrospinning led to heterogeneous mats. Addition of 30% of chloroform to the PPDL-HFIP mixture turned it into a transparent solution. After electrospinning, the PPDL-HFIP-chloroform mixtures yielded mats, which consisted of flat and round fibers with a wrinkled surface. The flat fibers (ribbons) were observed more frequently when the PPDL sample with the highest molecular weight was electrospun. All the obtained electrospun mats demonstrated high elongation at break (from 150% to 350%). In our future research, these mats will be examined as biomaterials.