The reaction features of the direct conversion of ethanol to butanol-1 and hexanol-1 in the presence of mono- and bimetallic active components based on Au and Cu supported on gamma-Al2O3 have been studied. It has been found that under conditions providing the supercritical state of ethanol, the reaction rate and selectivity in the presence of the Au-Cu/Al2O3 catalyst abruptly increases. In addition, a synergistic effect is observed: the yield of desired products over the Au-Cu catalyst is 6 or 14 times that over the Au or Cu monometallic counterpart, respectively. Differences in the catalytic behavior of the Au-Cu, Au-, and Cu-based systems have been discussed taking into account their structural features and the reaction mechanism.