The influence of molecular weight and the amount of the poly(vinylpyrrolidone) (PVP) on the growth of poly(vinylpyrrolidone)-based films on copper surfaces was studied by electrochemical, infrared and electronic spectroscopy, and thermogravimetric methods. Complex polymer/metal ions were deposited onto a copper surface, as the result of the electrochemically generated reaction of copper cations with PVP and SCN-, in sulfuric acid media. Spontaneous film growth on copper surfaces was generated and characterized as a Cu(II)/PVP/SCN- complex. Infrared spectra and thermal gravimetric curves of the films generated at + 0.7 V were compared with the chemically synthesized complex, and show the same patterns. The oxidation process can be described as: Cu(0)-> Cu(I) and Cu(I)-> Cu(II), and the copper complex formed at more positive potentials was characterized as Cu(II)/PVP/SCN-, with copper bonded to the oxygen atom of PVP and thiocyanate ligand N-linked. This study focuses on the complex formation on a copper surface in acid media and its characterization through electrochemical and spontaneously generated reactions. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2206-2214, 2009