Ethanol and isopropanol cross-condensation 0.2Au-0.06Ni/γ-Al2O3 catalyst have been developed based on the synergetic effect of gold and nickel in many reactions. A cross-condensation reaction results in the formation of pentanol-2 and pentanon-2 in high yields in the absence of any alkali or sacrificial agents (e.g., hydrogen acceptors or hydrogen donors). In this study, heterogeneous Au-Ni/Al2O3 catalysts were used in this type of reaction for the first time. The catalyst developed in this study is also effective for the self-condensation of ethanol, providing 85% selectivity of linear α-alcohols at 63.5% ethanol conversion. Structural investigations show that the morphological peculiarities and charge state of gold may produce the different activities of mono- and bimetallic Au- and Ni-containing catalysts.