Polycaprolactone/polypyrrole (PCL/PPy) fibers were prepared using an original approach by electrospinning a mixing solution of PCL and pyrrole monomer as the first step. The presence of pyrrole monomer inside the electrospun fibers was confirmed by Time-of-Flight secondary ion mass spectrometry (ToF-SIMS) analysis. Prepared fibers were immersed into the oxidizing agent solution containing pyrrole monomer and anionic surfactant surfactant - sodium 2-naphthalenesulfonate for polypyrrole coating at room temperature. The effect of preparation conditions was studied for the production of electrically conducting fabrics using various weight ratios of PCL to pyrrole monomer for fiber production. Various analytical methods were used to characterize the fibers before and after the polymerization. The presence of the polypyrrole coating on prepared PCL substructure was verified by Fourier Transform Infrared Spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and morphology analysis. The surface properties of the prepared conducting fibers were tested by contact angle measurement. The prepared nanofibers were homogenously coated with polypyrrole, and the samples containing at least 40 wt.% of pyrrole monomer after coating reached conductivity superior to 1 S/cm.