Electrospinning is a versatile and diverse technology for the production of nano-and microfibers that can be used as a drug delivery system (DDS). The aim of this study was to create fibrous scaffolds from a mixture of polycaprolactone (PCL) and polyethylene glycol (PEG) and to evaluate the suitability of the fibers as DDS. Dipyridamole (DPA), an anti-thrombotic and anti-proliferative pharmaceutical agent, was used as a model drug. Two types of PEG with different chain length were used. The structural, mechanical and physicochemical characteristics of the fibers with and without DPA, were determined, and the release kinetics of DPA were studied. The obtained fibers loaded with DPA and with the higher molecular weight PEG were smooth and had an average diameter of 586.75 ± 204.79 nm and an average Young's modulus of 57.14 ± 4.35 MPa, whereas the tensile strain at break was 0.61 ±0.05 mm/mm and the ultimate tensile strength (UTS) was 16.79 ± 3.08 MPa. The cumulative release of DPA revealed two stages: an initial burst phenomenon followed by slower Fickian diffusion (release exponent n = 0.432).