Electrochemical reduction of solution cast and self-assembled graphene oxide (GO) films on Au surfaces were studied using organic solvents. During the cyclic voltammetry measurements the structural changes in the films were recorded focusing on in situ infrared and Raman techniques. Both FT-Raman and dispersive Raman spectroscopy were utilized for the reduction studies. The spectroelectrochemical results indicate that the changes in the GO structure take place in a quite narrow potential range extending from −1 to −1.7 V. Higher negative potentials gives rise to reversible changes in the spectra and are not due to reduction processes of GO but more related to changes in the electrolyte media.