Biomimetic polymer nanofibers of poly(epsilon-caprolactone) and poly(L-lactide caprolactone) copolymer were prepared by electrospinning. Modifications of the polymer nanofibers aimed at improving their biomimetic properties were performed by two different routes: (1) immobilization of an adhesion peptide, which mimicked the adhesion sequence of the extracellular matrix protein fibronectin, on the polymer surface and (2) incorporation of self-complementary oligopeptides, which showed alternated hydrophilic and hydrophobic side chain groups and was capable of generating extended ordered structures by self-assembling, into the polymer nanofibers. The structure of the polymer/peptide nanofibers was investigated by X-ray photoelectron and Fourier transform infrared spectroscopies.