Discharging of aprotic sodium-oxygen (Na-O2) batteries is driven by the cathodic oxygen reduction reaction in the presence of sodium cations (Na+-ORR). However, the mechanism of aprotic Na+-ORR remains ambiguous and is system dependent. In-situ electrochemical Raman spectroscopy has been employed to study the aprotic Na+-ORR processes at three atomically ordered Au(hkl) single-crystal surfaces for the first time, and the structure-intermediates/mechanism relationship has been identified at a molecular level. Direct spectroscopic evidence of superoxide on Au(110) and peroxide on Au(100) and Au(111) as intermediates/products has been obtained. Combining these experimental results with theoretical simulation has revealed that the surface effect of Au(hkl) electrodes on aprotic Na+-ORR activity is mainly caused by the different adsorption of Na+ and O2. This work enhances our understanding of aprotic Na+-ORR on Au(hkl) surfaces and provides further guidance for the design of improved Na-O2 batteries.