Two different methods for solid-state electrochemical measurements in the absence of liquid electrolyte are discussed. The simplest approach is based on a two-electrode sandwich cell (without reference electrode), and it is suitable for ionically-conducting materials containing stable and chemically identifiable, mixed-valence redox sites (eg Fe(III,II) in Prussian Blue or Berlin Green). The second two-electrode design utilizes an ultramicrodisk working electrode which faces a large surface area silver-disk semireference/counter electrode. In order to discuss usefulness and limitations of these methods, we consider the following inorganic materials : Prussian Blue, Berlin Green, and silicotungstic acid single crystals. These structures contain mobile countercations (hydrated K+ or H+) in concentrations extensive enough to support diffusive transport of electrons hopping between Fe(III,II) or W(VI,V) centers (redox conduction). In the latter case, combination of potential step measurements in short-time and long-time experimental regimes provides an absolute electroanalytical method for determinations of redox centers and an effective diffusion coefficient for charge propagation.