In observing the electrocatalytic current of nanoparticles (NPs) using single-entity electrochemistry (SEE), the surface state of the NPs significantly influences the SEE signal. This study investigates the influence of capping agents on the electrocatalytic properties of gold (Au) NPs using SEE. Two inner-sphere reactions, hydrazine oxidation and glucose oxidation, were chosen to explore the SEE characteristics of Au NPs based on the capping agent presence. The results revealed that “capping agent-free” Au NPs exhibited signal magnitudes and frequencies consistent with theoretical expectations, indicating superior stability and catalytic performance in electrolyte solutions. In contrast, citrate-capped Au NPs showed signals varying depending on the applied potential, with larger magnitudes and lower frequencies than expected, likely due to an aggregation of NPs. This study suggests that capping agents play a crucial role in the catalytic performance and stability of Au NPs in SEE. By demonstrating that minimizing capping agent presence can enhance effectiveness in SEE, it provides insights into the future applications of NPs, particularly highlighting their potential as nanocatalysts in energy conversion reactions and environmental applications.