Understanding the hybrid charge-storage mechanisms of pseudocapacitive nanomaterials holds promising keys to further improve the performance of energy storage devices. Based on the dependence of the light scattering intensity of single Prussian blue nanoparticles (PBNPs) on their oxidation state during sinusoidal potential modulation at varying frequencies, we present an electro-optical microscopic imaging approach to optically acquire the Faradaic electrochemical impedance spectroscopy (oEIS) of single PBNPs. Here we reveal typical pseudocapacitive behavior with hybrid charge-storage mechanisms depending on the modulation frequency. In the low-frequency range, the optical amplitude is inversely proportional to the square root of the frequency (∆I ∝ f−0.5; diffusion-limited process), while in the high-frequency range, it is inversely proportional to the frequency (∆I ∝ f−1; surface charging process). Because the geometry of single cuboid-shaped PBNPs can be precisely determined by scanning electron microscopy and atomic force microscopy, oEIS of single PBNPs allows the determination of the depth of the surface charging layer, revealing it to be ~2 unit cells regardless of the nanoparticle size.