Poly(ε‐caprolactone)/polyvinylpyrrolidone (PCL/PVP) scaffolds with various composition were fabricated from 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) solution using the same electrospinning parameters in order to reveal the effect of polymer ratio on the material properties. The obtained materials were characterized using scanning electron microscopy, contact angle measurements, X‐ray diffraction, Fourier‐transformed infrared spectroscopy, and tensile testing. The strengthening effect of PVP was observed: Young modulus of PCL/PVP scaffold with 50/50 polymer ratio was found at 105.4 ± 8.4 MPa which is six times higher comparing to those of PCL scaffold. PVP‐containing scaffolds were extremely hydrophilic with PVP concentration of 5 wt% (vs. 25 wt% in previous reports) leading to full wetting of the material. in vitro studies showed an improved viability of HeLa cells cultured with the composites containing higher concentrations of PVP. Owing to the application of HFIP, PCL‐based materials were loaded with cyclophosphamide for the first time and the PVP‐containing materials demonstrated the intensified initial release of the model compound. Utilizing HFIP for the fabrication of PCL/PVP scaffolds significantly widens their application for drug delivery systems due to a good solubility of proteins, drugs, and other biologically active compounds in this solvent.