Thermoelectric generators (TEGs) convert a temperature difference into useful direct current (DC) power. TEGs are solid-state semiconductor devices that are generating a lot of interest for energy harvesting purposes in Internet of Things (IoT) applications. This paper analyzes the behavior of state-of-the-art TEGs designed for low temperature gradient operation, with special emphasis on IoT systems for health monitoring for high-voltage alternating current (AC) and DC applications. In such applications, the energy harvesting unit plays a leading role in supplying wireless sensors (WSs). An application example is also presented with the aim to monitor the health condition of devices installed in the tubular busbars found in electrical substations. Since substation busbars heat up due to the Joule effect, there is a small thermal gradient between the busbar and the ambient, so the TEG can convert this heat flow into useful DC energy to supply low-power WSs. This paper assesses the performance of different TEG devices for this application, where very low temperature gradients are expected. The results presented show that with temperature gradients as low as 5 °C it is possible to supply WSs.