Structural information has been gained during aerobic benzyl alcohol oxidation in "supercritical'' carbon dioxide at 150 bar on alumina-supported palladium by X-ray absorption spectroscopy while monitoring simultaneously the performance of the catalyst. The reduction of the catalyst by benzyl alcohol could be monitored by the analysis of the near-edge region of the Pd K-edge. The palladium constituent was mainly in metallic state under operating conditions. Partial reoxidation was observed when only oxygen in "supercritical'' carbon dioxide in the absence of alcohol was fed. The catalytic activity of the PdOx/Al2O3 catalyst during benzyl alcohol oxidation was comparable to that in a conventional continuous fixed-bed reactor and depended on the oxygen concentration in the feed. The rate of alcohol conversion went through a maximum when the oxygen concentration was increased. At maximum rate, part of the palladium was in the oxidized state. Upon further increase of the oxygen concentration, the activity decreased because of the formation of surface palladium oxide. The reaction rate in "supercritical'' carbon dioxide was strikingly higher than that observed for the corresponding liquid-phase oxidation.