Identifying the intermediate species in an electrocatalytic reaction can provide a great opportunity to understand the reaction mechanism and fabricate, a better catalyst. However, the direct observation of intermediate species at a single crystal-surface is. a daunting challenge for spectroscopic techniques. In this work, electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy (EC-SHINERS) is utilized to in situ monitor the electrooxidation processes at atomically flat Au(hkl) single crystal electrode surfaces: We systematically explored the effects,of crystallographic orientation, pH value, and anion on electrochemical behavior of intermediate (AuOH/AuO) species.. The experimental results are well Correlated, with our periodic density functional theory calculations and corroborate the long-standing speculation based on theoretical calculations in previous electrochemical studies. The presented in situ electrochemical SHINERS technique offers a unique way for a real-time investigation of an electrocatalytic reaction pathway at various well-defined noble metal surfaces.