Investigating the chemical nature of the adsorbed intermediate species on well-defined Cu single crystal substrates is crucial in understanding many electrocatalytic reactions. Herein, we systematically study the early stages of electrochemical oxidation of Cu(111) and polycrystalline Cu surfaces in different pH electrolytes using in situ shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). On Cu(111), for the first time, we identified surface OH species which convert to chemisorbed "O" before forming Cu2O in alkaline (0.01 M KOH) and neutral (0.1 M Na2SO4) electrolytes; while at the Cu(poly) surface, we only detected the presence of surface hydroxide. Whereas, in a strongly acidic solution (0.1 M H2SO4), sulfate replaces the hydroxyl/oxy species. This results improves the understanding of the reaction mechanisms of various electrocatalytic reactions.