In southern countries, including European states, solar collectors for additional water-heating systems are widely used. However, the disadvantage of such systems is that a considerable proportion of solar energy cannot be used with increasing water temperature and dissipates into the environment. It is proposed to use waste heat at a high temperature, which is supplied to a thermoelectric generator (TEG) operating on the basis of a temperature difference between the hot water in the solar collector and cold water supplied to a radiator on the other TEG side. This is a new application of thermoelectric converters, in which the converter can act not only as a source of electrical energy but also as a source of low-potential heat coming from the radiator. The total conversion efficiency in such devices can reach 90%. It is shown that the use of p -type legs in a TEG with the cleavage planes of the legs parallel to the heat-flux direction instead of the conventional parallel orientation results in an increase in the thermoelectric efficiency by 25% on average in the temperature range of 100–300°C.