Far infrared spectra of the surface films formed upon anodic oxidation of copper have been obtained in-situ for the first time in aqueous solution environments using a synchrotron source. The spectroelectrochemical behavior of copper was studied in NaOH and in a dilute solution of KSCN in perchlorate. The oxide film at - 0.05 V vs. SCE in 0.1 M NaOH solution has been identified as Cu2O. In the passive region at 0.3 V, CuO and Cu(OH), appear to be present on the surface. Vibrational bands observed in 0.025 M KSCN + perchlorate solution are attributed to a multilayer film of copper(I) thiocyanate.