Potential of zero charge (PZC) is a fundamental quantity that dictates the structure of the electrical double layer. Studies using single crystals suggest a polycrystalline surface should display an inhomogeneous distribution of PZC and electric field, which directly affects the electrochemical energy storage and conversion processes occurring at the electrode-electrolyte interface. Herein, we demonstrate the direct mapping of local PZC using scanning electrochemical cell microscopy (SECCM). The potential-dependent charging current upon the formation of the microscopic electrode-electrolyte interface is used to determine the PZC. Using polycrystalline Pt as a model system, correlative SECCM and electron backscatter diffraction (EBSD) images show the dependence of PZC on the local crystal grain orientation. The electrocatalytic activity can be mapped from the same SECCM experiment via local voltammetry, which demonstrates the variation of hydrogen evolution reaction (HER) activity across Pt grains. The method reported here can be readily applied to study other electrochemical interfaces, providing rich correlative information on the surface property and electrocatalytic activities.