The aim of this work was to investigate the influence of morphology on its electrochemical properties by comparing ZnO nanostructures in the forms of tetrapods of different sizes, nanorods, and nanoparticles. ZnO tetrapods were prepared by the combustion method and separated into two fractions by size, ruling out the influence of synthesis conditions. Structural and morphological properties of different ZnO nanostructure morphologies were identified by using various characterization techniques: scanning and transmission electron microscopies (SEM and TEM), X-ray powder diffraction (XRD), nitrogen adsorption/desorption measurements at 77 K, and UV-vis spectroscopy (UV-vis). Analysis of electrochemical properties showed the highest active surface area of 0.095 cm2 and the lowest peak separation value of 61.7 mV for large ZnO tetrapods, which are close to the theoretical values. The correlation between the pore size in different ZnO nanostructures because of packing and their electrochemical properties is established. We expect that the detailed analysis of ZnO nanostructures conducted in this study will be advantageous for future electrochemical and biosensing applications of these materials.