Polymeric scaffolds prepared from polycaprolactone (PCL), PCL-collagen and PCL-elastin were prepared by electrospinning. The scaffolds were coated by plasma polymerization of pyrrole doped with iodine, to improve cellular adhesion and fibroblast proliferation. The morphology, composition, and crystalline structure of the scaffolds were characterized by scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy, small- and wide-angle X-ray scattering, thermogravimetric analysis and differential scanning calorimetry. The scaffold fibers had average diameters between 90 and 330 nm before coating. After coating by plasma polymerization, the average diameters increased to between 290 and 530 nm. The presence of elastin and collagen in the fibers was corroborated by infrared spectroscopy. X-ray scattering measurements show that neither elastin nor collagen form crystals in the fiber, while PCL maintains its crystallinity and is not affected by the plasma treatment. Fibroblast cell cultures in the presence of the scaffolds were characterized by viability assays and SEM. The results show that the scaffolds modified with plasma polymerized pyrrole provide a suitable environment for fibroblast adhesion, growth and viability.