Surface decoration of metal oxides by metals for enhancing their electrocatalytic properties for organic conversions has attracted a lot of researchers' interest due to their high abundancy, inexpensiveness, and high stability. In the present work, a process for the synthesis of black gold (BG) using a citrate assisted chemical route and m-ZrO2 by a hydrothermal method at 200 °C has been developed. Further, different concentrations of black gold are being used to decorate the surface of zirconia by exploitation of surface potential of zirconia and gold surfaces. The catalyst having 6 mol % concentration of black gold shows excellent electrocatalytic activity for ethanol oxidation with low oxidation peak potential (1.17 V) and high peak current density (8.54 mA cm-2). The current density ratio (jf/jb) is also high (2.54) for this catalyst indicating its high tolerance toward poisoning by intermediate species generated during the catalytic cycle. The enhanced electrocatalytic activity can be attributed to the high tolerance of gold toward CO poisoning and high stability of the ZrO2 support. The black gold decorated zirconia catalyst showed enhanced activity during photoelectrochemical studies when the entire spectrum of light falls on the catalyst. Ultrafast transient studies demonstrated plasmonic excitation of metallic free electrons and subsequent charge separation in the black gold-ZrO2 heterointerface as the key factor for enhanced photoelectrocatalytic activity.