The utilization of two-dimensional (2D) materials within electrochemical devices constitutes a pivotal area of investigation, particularly pertinent to energy-related materials. Scanning electrochemical cell microscopy (SECCM) stands as a valuable characterization tool for the in-situ visualization of electrochemical processes transpiring within nanoscale structures. In the context of this investigation, SECCM was employed to scrutinize the influence of atomic structures in multilayer graphene and graphite samples, emblematic of 2D materials, upon a spectrum of electrochemical reactions, encompassing redox reactions of Ru(NH3)63+/2+. By visualizing and locally evaluating electrochemical reactions with various atomic structures, this research can be applied to design materials to promote more electrochemical reactions, as well as to other electrochemical energy devices (such as lithium-ion batteries and electrocatalysts). Furthermore, it extends its purview to assess the applicability of graphene substrates as platforms for the evaluation of other two-dimensional materials.