It was found that, if the energy released in the formation of product molecules in a heterogeneous reaction was smaller than the work function of the surface, the current density of the chemiemission of electrons from the surface of any semiconductor satisfied the condition j ≈ Bexp(βE), where B and β are coefficients and E is the electric field in the semiconductor surface plane. A mathematical model describing the transfer of hot metal electrons excited in a catalytic reaction through the metal-gas interphase boundary was studied. The parameters of the system at which a study of the distribution of catalytic centers over the surface of a metal or semiconductor by the scanning tip method on the basis of the chemiemission of electrons stimulated by an electric field was possible (resolution δr ∼ 10−8–10−7 m) were determined. Theoretical results corresponded to the experimental data obtained using weak electric fields (0 < E < 5 × 106 V/m) for the heterogeneous recombination of hydrogen atoms on the surface of calcium, titanium, and n-type silicon.