During anodic current operation (I = 0.6 mu A) at 315 degrees C of a O-2, Pt/ZrO2 (8 mol % Y2O3/Ag, O-2 galvanic cell, we have detected Raman scattered photons from the Pt electrode. The corresponding bands have been assigned to the transient formation of Pt-O bonds with an unusually low vibrational frequency. The temporal evolution of the signals, at a constant value of current intensity, temperature, and oxygen flow conditions, has been related to the migration (spillover) of oxygen species from the solid electrolyte-metal-gaseous oxygen three-phase boundary zone onto the porous Pt electrode. These observation give direct information about oxygen atom motion which results from the O2- ions pumping toward the working electrode under conditions in which the non-Faradaic electrochemical modification of catalytic activity has been observed.