A sol–gel strategy is developed to fabricate highly regular Au nanoelectrode arrays (NEAs) consisting of a nanoperforated ultrathin membrane of ZrO2, which exhibits a well-ordered array of pores (65±5) nm in diameter with a mean center-to-center distance of (110±10) nm, on a polycrystalline gold surface. The structural properties are investigated by field-emission scanning electron microscopy (FE-SEM), while grazing incidence small-angle X-ray scattering (GISAXS) is used to assess the thickness homogeneity and the period of the array of electrodes. In addition, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) are carried out to describe quantitatively the accessibility, electrochemical behavior, and diffusion processes of the gold NEA. A model applying parameters obtained from FE-SEM, CV, and EIS analyses is proposed to simulate the experimental results. A fairly good agreement between the experimental and the simulated data is obtained, thus allowing the deconvolution of the different diffusion regimes at the NEA.