This work presents the coupling relationship between the flame emission spectra and explosion characteristics of CH 4 /C 2 H 6 /air mixtures ([CH 4 ] = 7.0, 9.5, and 11.0 vol %; [C 2 H 6 ] = 0−2.0 vol %). A 20 L spherical explosion testing system was used to record the explosion pressure−time curves of the CH 4 /C 2 H 6 /air mixtures at room temperature (18−22 °C) and pressure (1 atm). A flame emission detection system was used to capture the emission spectra of H* and OH* during the gas mixture explosions. In addition, sensitivity analysis was carried out on the change in the mole fraction of the explosion intermediates in a detailed mechanism (GRI-Mech 3.0). The results demonstrate that P max and (dP/dt) max increased with the addition of C 2 H 6 for the fuel-lean state, while the time to reach P max decreased with the addition of C 2 H 6 . For the stoichiometric and fuel-rich states, the opposite was true. Additionally, the trends of P max , (dP/dt) max , and time to reach P max are essentially in accordance with those of I max , (dI/dt) max , and time to reach I max for H* and OH*. Furthermore, on the basis of the sensitivity analysis, the C 2 H 6 addition has a positive effect on the production of OH* at the time corresponding to (dP/dt) max for the fuellean state, while the formation of OH* is inhibited by C 2 H 6 at the time to reach (dP/dt) max for the stoichiometric and fuel-rich states, which is consistent with the experimental results.