Thermoelectric Generators (TEGs) are devices for direct conversion of heat into electrical power and bear a great potential for applications in energy scavenging and green energy harvesting. Given a heat source, the conversion efficiency depends on the available temperature difference, and must be maximized for optimal operation of the TEG. In this frame, the choice of materials with high thermoelectric properties should be accompanied by the identification of criteria for an optimal exploitation of the electrical power output. In this work, we briefly review the main properties of TEGs, focusing on the electrical power output and the thermal-to-electrical conversion efficiency. Besides, we discuss principles of operation of TEGs enabling the optimization of the electrical power output, based on the suitable choice of the electrical load. In particular, we comparatively present and discuss the conditions for matching the electrical load—yielding to maximum power transfer—and those for maximizing the conversion efficiency. We compare the two conditions applying them to the exploitation of a heat reservoir for energy storage and to the recovery of heat from a heat exchanger. We conclude that the difference between the two conditions is not significant enough to justify the complexity required by the implementation of the maximum efficiency. In addition, we consider the effect of the thermal contact resistance on the electrical power output. Using a simple thermal-electrical model, we demonstrate that the equivalent electrical resistance measured between the terminals of the TEG depends on the thermal exchange. Hence, for maximum power transfer, the electrical load of the TEG should not match its parasitic resistance, but the equivalent electrical resistance in each specific operating conditions, which determine the thermal fluxes. The model can be applied for the development of efficient alternative algorithms for maximum power point tracking.