Here, we present a quantitative method to measure the concentration and diffusivity of Li ion in a solid-state electrolyte with nanoscale depth resolution. We designed a standard sample with different depths of trenches and used time-of-flight secondary ion mass spectroscopy, inductively coupled plasma optical emission spectroscopy, three-dimensional (3D) optical microscopy, and electrochemical strain microscopy to obtain effective Li-ion concentration and the corresponding diffusivity as a function of depth. As a result, we verified the dependence of electromechanical strain induced by ionic oscillation on mobile-ion concentration. We also showed the diffusivity change as a function of effective concentration and discussed the difference in diffusivity near the surface and inside the bulk. Our method can be widely used for electromechanical strain in various ionic conductors, rendering our technique universal for quantitative analysis of ionic dynamics at a multiscale.