Scanning electrochemical cell microscopy (SECCM) is used to map anodic and cathodic processes on polycrystalline zinc in 10 mM H2SO4, at the nanoscale. Electrochemical maps are correlated directly with structural data from electron backscatter diffraction applied to the same regions of the surface, and density functional theory (DFT) calculations are used to rationalize the data. Preliminary data on droplet stability with SECCM point measurements indicated that there was a significant spreading of the meniscus cell with an air atmosphere, attributed to changes in pH during the oxygen reduction reaction, compromising the lateral resolution of the SECCM measurement. Experiments with an argon atmosphere, as well as the application of a hydrophobic n-dodecane oil layer on the Zn interface, prevented spreading. Electrochemical maps of polycrystalline Zn surface under an Ar atmosphere indicated that the hydrogen evolution reaction (HER) and Zn electrodissolution on individual low-index grains decreased in the order (1¯21¯0) ≫ (011¯0) > (0001). DFT calculations revealed a correlation between experimental values of current associated with HER and Zn dissolution reactions and the predicted hydrogen adsorption and Zn dissolution energies on individual facets, respectively. This work further advances SECCM as a technique for probing electrified interfaces and demonstrates its applicability to reactive metals.