The main features of the mechanism of selective reduction of nitrogen oxides by hydrocarbons (methane, propane, and propylene) in excess oxygen catalyzed by systems containing transition metal cations are considered. A combination of steady-state and non-steady-state kinetic studies, in situ Fourier-transform infrared (FTIR) spectroscopy, temperature-programmed desorption, and theoretical analysis of bond strengths and spectral data for adsorption complexes made it possible to determine reliably that surface nitrate complexes are key intermediates at real temperatures of catalysis. The rate-limiting step in these reactions includes the interaction of these complexes with hydrocarbons or their activated forms. Factors are considered that determine the structure, bond strength, and routes of nitrate complexes transformations under the action of hydrocarbons. Mechanistic schemes are proposed for the reaction of various types of hydrocarbons in which the determining role belongs to the formation of organic nitro compounds in a rate-limiting step. Their further fast transformation with the participation of surface acid sites resulting in the formation of ammonia, which is a highly efficient reducing agent, though not limiting the whole process, but determines nevertheless both the selectivity to the target product, molecular nitrogen, and the selectivity of hydrocarbon consumption for nitrogen oxide reduction.