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The study of thermoelectric properties of crystalline semiconductors with structural defects is of practical interest in the development of radiation-resistant Peltier elements. In this case, the spectrum of energy levels of hydrogen-like impurities and intrinsic point defects in the band gap (energy gap) of crystal plays an important role. The purpose of this work is to analyze the features of the single-electron band model of semiconductors with hopping electron migration both via atoms of hydrogen-like impurities and via their own point triplecharged intrinsic defects in the c- and v-bands, as well as to search for the possibility of their use in the Peltier element in the temperature range, when the transitions of electrons and holes from impurity atoms and/or intrinsic defects to the c- and v-bands can be neglected. For Peltier elements with electron hopping migration we propose: (i) an h-diode containing |d1)- and |d2)-regions with hydrogen-like donors of two types in the charge states (0) and (+1) and compensating them hydrogen-like acceptors in the charge state (−1); (ii) a homogeneous semiconductor containing intrinsic t-defects in the charge states (−1, 0, +1), as well as ions of donors and acceptors to control the distribution of t-defects over the charge states. The band diagrams of the proposed Peltier elements in equilibrium and upon excitation of a stationary hopping electric current are analyzed. A model of the h-diode containing hydrogen-like donors of two types |d1) and |d2) with hopping migration of electrons between them for 50 % compensation by acceptors is considered. It is shown that in the case of the reverse (forward) electrical bias of the diode, the cooling (heating) of the region of the electric double layer between |d1)- and |d2)-regions is possible. A Peltier element based on a semiconductor with point t-defects is considered. It is assumed that the temperature and the concentration of ions of hydrogen-like acceptors and donors are to assure all t-defects to be in the charge state (0). It is shown that in such an element it is possible to cool down the metal semiconductor contact under a negative electric potential and to heat up the opposite contact under a positive potential.