The development of solid-state materials used in rechargeable lithium batteries, i.e., electrode materials (positive and negative as well) and solid-state electrolytes, requires knowledge of their transport properties, i.e., electrical and electrochemical properties. This chapter provides an overview of the various techniques used for the characterizations of thermodynamics and kinetics of the solid-state phases. DCExperimental methodsdc techniques and AC techniquesExperimental methodsac techniques are presented and discussed including methods for evaluating the semiconducting or metallic character of electrodes. MeasurementsTransference numbermeasurements of the transference number, electrochemical stability windowElectrochemical Stability Window (ESW) and diffusion coefficient are also examined and some examples are provided.