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In this study, we developed clean Cu nanoparticles with tailored curvatures to modulate the local concentration of K<jats:sup>+<\/jats:sup> cations and investigate their effects on CO<jats:sub>2<\/jats:sub>RR. The adjustment of particle curvature allows for direct control over cation concentrations within the electrochemical double layer, enabling broad\u2010range modulation of cation concentration without concerns regarding solubility limitations or anionic interference. By tuning the plasmonic modes of the Cu particles, we achieved highly sensitive surface\u2010enhanced Raman spectroscopy (SERS) under resonant conditions, facilitating in situ tracking of the short\u2010lived intermediates in CO<jats:sub>2<\/jats:sub>RR. Our results revealed that K<jats:sup>+<\/jats:sup> cations not only stabilize *COOH and *CO species and reduce the reaction energy barrier for C\u2500C coupling but also increase the surface coverage of *CO, particularly for bridge *CO configurations. 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