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A new experimental set-up, coupling electrochemistry and mass spectroscopic techniques, for the investigation of a solid electrochemical cell under high vacuum conditions (HV) is presented. Two configurations are realized allowing the investigation of both the electrochemical and electrocatalytical behavior of a thin Pt layer on yttria stabilized zirconia (YSZ). We can readily select the atmosphere down to 10(-6) Pa partial pressure and determine the response of the system in less than 1 s. Under HV conditions, YSZ appears electrochemically active and we have identified, in the cathodic potential domain, the reduction/oxidation process of zirconia and in the anodic domain, the platinum oxidation/reduction and the oxygen evolution reactions. In a catalytic active gas mixture, despite the Faradaic enhancement of the CO oxidation observed over Pt/YSZ during an anodic polarization, an intriguing sustainable enhanced Pt/YSZ catalyst activity is achieved after current interruption.