In this chapter, the “state of art” in the computational fluid dynamics (CFD) modeling of ignition and after ignition processes based on the detailed chemical approach is discussed. Initially, attention is paid to simulate the ignition of gaseous hydrogen/air mixtures with regards to problems of turbulent flame acceleration in closed compartments. The modeling capabilities are then illustrated by the results of liquid fuel injections into the combustion volume. In this case, the ignition processes are complicated by a presence of sprays, droplet formation, and evaporation. The autoignition of pure gaseous mixtures, considered as a fragment of the complete problem formulation, is also analyzed. In this case, different chemical mechanisms were constructed and validated for fuels used in the automotive industry, namely diesel oil, gasoline, ethanol, and some biofuels (methyl esters, e.g., rapeseed methyl ester) based on the concept of fuel surrogates. The tools used in this study are three‐dimensional CFD, KIVA3V rel.2 and FOAM, codes. The near‐identical numerical and physical models were formulated for both codes, for a test case of autoignition processes, when the liquid sprays were injected into the constant volume vessel, and numerical results compared between themselves and experimental data on the flame lift‐off lengths and autoignition times. The flame lift‐off phenomenon was interpreted as a consequence of the ignition process. The spark ignition process was then simulated for the spark‐ignition gasoline engine boosted by a direct ethanol injection. Finally, the ignition and combustion of solid aluminum was analyzed in water/steam and carbon dioxide environment, with the application to advanced energy generation systems.