The polarization response of a coplanar electrochemical capacitor covered with an ionic liquid as the electrolyte has been examined using a combination of two powerful analytic techniques, X-ray photoelectron spectroscopy (XPS) and scanning electron microcopy (SEM). Spatiotemporal distribution of the ionic liquid surface potential, upon DC or AC (square wave) biasing, has been monitored via chemical element binding energy shifts using XPS and secondary electron intensity variations using SEM. SEM's high spatial resolution and speedy imaging together with application of a data mining algorithm made mapping of the surface potential distribution across the capacitor possible. Interestingly, despite the differences in the detection principles, both techniques yield similar polarization relaxation time constants. The results demonstrate the power of a synergistic combination of the two techniques with complementary capabilities and pave the way to a deeper understanding of liquid/solid interfaces and for performance evaluation and diagnostics of electrochemical devices.