Excitation of a luminescence by highly exothermic chemical reaction on the surface of a luminophore provides a unique opportunity to separate surface luminescence from the bulk luminescence. This enables studies of the electronic properties of the semiconductor surfaces even if the surfaces are of complicate shapes. We have studied heterogeneous chemiluminescence (HCL) of ZnO powders. The luminescence was excited by a release of chemical energy, namely by catalytic recombination of hydrogen atoms. The HCL spectra were compared to the photoluminescence (PL) spectra. The HCL spectra were sensitive to the details of preparation and treatment whereas PL spectra almost did not change. HCL spectra of powder samples pretreated for enhancing “green” luminescence exhibited long-wavelength tail (up to 800 nm) and their maximum was blue-shifted as compared with PL spectra. Different HCL bands forming long-wavelength tail were isolated by changing the temperature of the samples. Additional milling of ZnO led to amplification of the HCL-specific surface bands. Pure ZnO showed neither PL nor HCL; however we were able to observe HCL surface bands with maxima at 610 nm and 730 nm after treatment of the sample in atomic hydrogen atmosphere at 570 K. Remarkably, such treatment did not cause appearance of the PL. The HCL in the presence of atomic hydrogen was steady in time and was caused by an abstraction of adsorbed hydrogen by incident hydrogen atoms, i.e. the reaction followed Eley-Rideal mechanism. The HCL can be utilized for in situ monitoring of the growth and evolution of ZnO in controlled atmosphere.