While single nanoparticle electrochemistry holds great promise for establishing the structure-activity relationship (SAR) of electroactive nanomaterials, as it removes the heterogeneity among individuals, successful SAR studies remain rare. When one nanoparticle is seen to exhibit better performance than the others, it is often simply attributed to better activity of the particular individual. By taking the ion insertion reaction of Prussian blue nanoparticles as an example, here we show that the electrical contact between nanoparticles and electrode, a previously overlooked factor, was greatly distinct from one nanoparticle to another and significantly contributed to the apparent heterogeneity in the reactivity and cyclability. An individual nanoparticle with intrinsically perfect structure (size, facet, crystallinity, and so on) could be completely inactive, simply due to poor electrical contacts, which blurred the SAR and likely caused failures. We further proposed a sputter-coating method to enhance the electrical contacts by depositing an ultrathin platinum layer onto the sample. Such an approach was routinely adopted in scanning electron microscopy to improve the electron mobility between nanoparticles and substrate. Elimination of heterogeneous contacts ensured that the electrochemical activity of single nanoparticles can be accessed and further correlated with their structural features, thus paving the way for single nanoparticle electrochemistry to deliver on its promises in SAR.