A critical and detailed assessment of using Shell Isolated Nanoparticles for Enhanced Raman Spectroscopy (SHINERS) on different electrode substrates was carried out, providing relative enhancement factors, as well as an evaluation of the distribution of shell-isolated nanoparticles upon the electrode surfaces. The chemical makeup of surface layers formed upon lithium metal electrodes and the mechanism of the oxygen reduction reaction on carbon substrates relevant to lithium–oxygen cells are studied with the employment of the SHINERS technique. SHINERS enhanced the Raman signal at these surfaces showing a predominant Li₂O based layer on lithium metal in a variety of electrolytes. The formation of LiO₂and Li₂O₂, as well as degradation reactions forming Li₂CO₃, upon planar carbon electrode interfaces and upon composite carbon black electrodes were followed under potential control during the reduction of oxygen in a non-aqueous electrolyte based on dimethyl sulfoxide.