The aim of this work was to obtain polymer fibers by the emulsion electrospinning. For this purpose, polycaprolactone (PCL) was used, which was modified before the electrospinning stage with micelles obtained by the oil-in-water (O/W) emulsion method. Micelles were obtained by combining the non-ionic surfactant Tween 80 or Triton X-100 used at different concentrations with the amino acid alanine. The obtained fibrous substrates had a typical unimodal fiber size distribution and their average size was in the range of 590-800 nm. The effectiveness of the emulsion electrospinning process was confirmed by Fourier Transform Infrared Spectroscopy - Attenuated Total Reflectance (FTIR-ATR) showing the presence of surfactants. The addition of micelles to the polymer solution significantly reduces the contact angle of nonwoven fabrics: from 120° (for PCL) to ~20-30° for surfactant-loaded nonwovens, and the micellar form allows tracking the release of alanine into the solution (UV-Vis). The combination of the core-shell-morphology of the emulsion electrospun fibers allows comparable amino acid release times. There were no significant differences in both the amount of alanine released and the rate of its release between PCL/Tween80/alanine and PCL/Triton X-100/alanine fibers, which were characterized by a similar fiber size.