Chemiluminescence emissions measurements of OH* and CH* are used to characterize the combustion of blends of methane and hydrogen in air in a constant volume combustion bomb, with two sets of initial conditions. The combined results of combustion development cover from 0.1 to 2.5 MPa. Burning velocity, heat release and unburned/burned gas temperatures are obtained from the pressure by using a two-zone thermodynamic combustion diagnostic model. Intensity of OH* and CH* increases with the initial temperature and the percentage of hydrogen, in parallel with the usual increase in burning velocity. The timings of the peaks of OH* and CH* chemiluminescence emissions are found to correlate respectively with the maximum rate of heat release and flame temperature. These results show that both chemiluminescence signals can be used to monitorize the burning process in combustion devices operating in the pressure range studied. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.