The process of combustion of a liquid fuel layer (diesel, kerosene, gasoline, separated petroleum, and oil) in the presence of CO2 hydrate has been studied. These fuels are widely used in engineering, which explains the great interest in effective methods of extinguishing. Extinguishing liquid fuels is quite a complicated scientific and technical task. It is often necessary to deal with fire extinction during oil spills and at fuel burning in large containers outdoors and in warehouses. Recently, attention to new extinguishing methods has increased. Advances in technology of the production, storage, and transportation of inert gas hydrates enhance the opportunities of using CO2 hydrate for extinguishing liquid fuels. Previous studies have shown a fairly high efficiency of CO2 hydrate (compared to water spray) in the extinction of volumetric fires. To date, there are neither experimental data nor methods for determining the dissociation rate of CO2 hydrate powder at the time of the gas hydrate fall on the burning layer of liquid fuel. The value of the dissociation rate is important to know in order to determine the temperatures of stable combustion and, accordingly, the mass of CO2 hydrate required to extinguish the flame. For the first time, a method jointly accounting for both the combustion of liquid fuel and the dissociation rate of the falling powder of gas hydrate at a negative temperature is proposed. The combustion stability depends on many factors. This paper defines three characteristic modes of evaporation of a liquid fuel layer, depending on the prevalence of vapor diffusion or free gas convection. The influence of the diameter and height of the layer on the nature of fuel evaporation is investigated.