Interaction of copper(I)-polypyrrole (PPy) complexes prepared by dissolving excess bulk Cu from PPy and leaving the Cu+ within PPy was investigated. The Cu-PPy interaction resulting from an electron transfer from the Cu atom to the PPy was determined from surface-enhanced Raman spectroscopy (SERS) and X-ray photoelectron spectroscopy (XPS) analyses. There is one Cu+ for circa 6 pyrrole monomers estimated from the difference of the charges of Cu deposition and dissolution, the dissolving curves of cyclic voltammetry (CV) voltammograms, and the XPS analysis.