Comparative results of studying the oxidative dehydrogenation of ethane (ODE) on catalytic vanadium-phosphorus oxide systems deposited by the molecular layering method on the surface of oxide supports (Al2O3, SiO2) have been presented. It has been found that the highest activity in ODE and selectivity for ethylene are exhibited by vanadium-phosphorus-containing catalysts. The influence of the acidity of catalytic systems on the activity and selectivity of the process has been revealed. The selectivity of the ODE process for ethylene reaches 90%. An increase in the oxygen concentration in the initial mixture from 3.5 to 20% leads mainly to a decrease in the selectivity of the ODE process with respect to the ethylene yield.