Molecular understanding of the electrochemical oxidation of metals and the electro-reduction of metal oxides is of pivotal importance for the rational design of catalyst-based devices where metal(oxide) electrodes play a crucial role. Operando monitoring and reliable identification of reacting species, however, are challenging tasks because they require surface-molecular sensitive and specific experiments under reaction conditions and sophisticated theoretical calculations. The lack of molecular insight under operating conditions is largely due to the limited availability of operando tools and to date still hinders a quick technological advancement of electrocatalytic devices. Here, we present a combination of advanced density functional theory (DFT) calculations considering implicit solvent contributions and time-resolved electrochemical surface-enhanced Raman spectroscopy (EC-SERS) to identify short-lived reaction intermediates during the showcase electro-reduction of Au oxide (AuOx) in sulfuric acid over several tens of seconds. The EC-SER spectra provide evidence for temporary Au-OH formation and for the asynchronous adsorption of (bi)sulfate ions at the surface during the reduction process. Spectral intensity fluctuations indicate an OH/(bi)sulfate turnover period of 4 s. As such, the presented EC-SERS potential jump approach combined with implicit solvent DFT simulations allows us to propose a reaction mechanism and prove that short-lived Au-OH intermediates also play an active role during the AuOx electro-reduction in acidic media, implying their potential relevance also for other electrocatalytic systems operating at low pH, like metal corrosion, the oxidation of CO, HCOOH, and other small organic molecules, and the oxygen evolution reaction.