Thermoelectric (TE) generators provide electrical energy from direct conversion of heat by means of the Seebeck effect; without moving parts, completely silent, and with negligible maintenance. As any other heat engine this conversion exploits only a fraction of the Carnot efficiency (Rowe (ed.), CRC Handbook of Thermoelectrics (CRC Press Inc., 1995), p. 19 1). The TE efficiency is linked to the thermoelectric figure of merit Z, which itself is given by basic material properties: Z = S2σ/κ. These are the electrical conductivity σ, the thermal conductivity κ and the Seebeck coefficient or thermopower S, which is known as the factor of proportionality between voltage output and applied temperature difference in a given TE sample. A distinct sensitivity to the carrier concentration and structural variations make the control and stabilisation of thermopower very challenging in complex material structures since degradation by diffusion, decomposition or evaporation can be observed in many cases during synthesis, operation and even in the process of characterisation of TE semiconductors; particularly at elevated temperatures. Investigating structural and compositional properties, stability, and performance of TE materials, and consequently aiming to understand their interaction, mainly methods like X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), scanning electron microscopy (SEM) or integral temperature dependent measurements of particular transport properties are used. Although TE materials research satisfies highest requirements on accuracy, the above mentioned techniques are not perfectly qualified to investigate promising material classes thoroughly. Against the background of usually complex material structures this article aims to show, that an efficient characterisation of TE materials becomes accessible for several questions by use of a spatially resolved determination of the thermopower.