Ion transport is a fundamental process in many physical, chemical, and biological phenomena, and especially in electrochemical energy conversion and storage. Despite its immense importance, demonstrations of label-free, spatially and temporally resolved ion imaging in the solution phase under operando conditions are not widespread. Here we spatiotemporally map ion concentration gradient evolution in solution and yield ion transport parameters by refining interferometric reflection microscopy, obviating the need for absorptive or fluorescent labels. As an example, we use an electrochemical cell with planar electrodes to drive concentration gradients in a ferricyanide-based aqueous redox electrolyte, and we observe the lateral spatiotemporal evolution of ions via concentration-dependent changes to the refractive index. Analysis of an evolving spatiotemporal ion distribution directly yields the diffusivity of the redox-active species. The simplicity of this approach makes it amenable to probing local ion transport behavior in a wide range of electrochemical, bioelectronic, and electrophysiological systems.