The biodegradable electrospun nanofibers are ideal candidates for for wound healing, tissue engineering and other biomedical applications thanks to their nanostructure that is similar to the extracellular matrix. However, the preparation of electrospun nanofibers with sufficiently good mechanical properties, good bio-compatibility and biodegradability can be challenging. In this work the polycaprolactone/polyethylene glycol (PCL/PEG) electrospun nanofibers were prepared by electrospinning of the PCL/PEG solutions containing various ratios of PCL:PEG polymers ranging from 5:95 to 75:25. The PCL:PEG ratio influenced the biodegradability and the mechanical properties of the nanofibers because an increase of the PEG percentage led to a decrease of the fibers strength and an increase of the degradation rate in water. The biocompatibility of the nanofibers was improved by deposition of thin amine layers by means of the cyclopropylamine plasma polymerization in RF capacitively coupled discharge. The XPS analysis revealed that the amine layer was deposited through the entire nanofibrous mesh. The presence of the amine groups is supposed to enhance the adhesion and proliferation of the cells, thus enhancing the properties of nanofibers for biomedical applications.