Rate-controlled constrained-equilibrium method has been further developed to model methane/air combustion. A set of constraints has been identified to predict the nonequilibrium evolution of the combustion process. The set predicts the ignition delay times of the corresponding detailed kinetic model to within 10% of accuracy over a wide range of initial temperatures (900 K–1200 K), initial pressures (1 atm–50 atm) and equivalence ratios (0.6–1.2). It also predicts the experimental shock tube ignition delay times favorably well. Direct integration of the rate equations for the constraint potentials has been employed. Once the values of the potentials are obtained, the concentration of all species can be calculated. The underlying detailed kinetic model involves 352 reactions among 60 H/O/N/C1-2 species, hence 60 rate equations, while the RCCE calculations involve 16 total constraints, thus 16 total rate equations. Nonetheless, the constrained-equilibrium concentrations of all 60 species are calculated at any time step subject to the 16 constraints.