Gold　(Au)　can　be　used　as　an　ideal　metal　electrocatalyst　for　ethanol　and　glucose　oxidation　reactions　due　to　its　high　performance-to-cost　ratio.　In　this　paper,　the　Au　aerogel　with　high-index　facets　was　synthesized　by　using　the　laser　ablation　in　liquid　technology,　which　can　improve　the　electrocatalytic　activity　of　Au.　The　as-prepared　Au　aerogel　showed　excellent　mass　activity　and　specific　activity　toward　ethanol　oxidation　reaction,　which　are　4.6　times　and　2.1　times　higher　than　Au/C,　respectively.　The　3D　porous　nature　and　rich　defect　of　the　Au　aerogel　provide　more　active　sites.　In　addition,　the　high-index　facets　with　under-coordinated　atoms　enhance　the　adsorption　of　ethanol　and　glucose　molecules,　thus　improving　the　intrinsic　catalytic　activity　of　Au　aerogel.　The　effect　of　high-index　facets　has　also　been　investigated　by　density　functional　theory　calculations.　Furthermore,　the　Au　aerogels　also　show　good　electrocatalytic　activity　and　stability　toward　glucose　oxidation　reaction.　These　results　are　conducive　to　promote　the　practical　application　of　Au　in　electrocatalysis.