The demand for gas turbines that accept a variety of fuels has continuously increased over the last decade. Understanding the effects of varying fuel compositions on combustion characteristics and emissions is critical to designing fuel-flexible combustors. In this study, the combustion characteristics and emissions of methane and hydrogen-enriched methane were both experimentally and numerically investigated under ultra-lean conditions (O0.5). This study was performed using global mechanisms with a one-step mechanism by Westbrook and Dryer and a two-step mechanism with an irreversible and reversible CO/CO2 step (2sCM1 and 2sCM2). Results show that the 2sCM2 mechanism under-predicted the temperature, major species, and NOx by more than 100% under ultra-lean conditions; thus, we proposed a modified-2sCM2 mechanism to better simulate the combustion characteristics. The mechanisms of Westbrook, 2sCM1, and modified 2sCM2 predicted the temperature and the CO2 emission with an average deviation of about 5% from the experimental values. Westbrook and 2sCM1, however, over-predicted the NOx emission by approximately 81% and 152%, respectively, as compared with an average under-prediction of 11% by the modified-2sCM2 mechanism. The numerical results using the proposed modified-2sCM2 mechanism shows that the presence of hydrogen in the fuel mixture inhibits the oxidation of methane that led to the formation of unburned hydrocarbons in the flame. We also showed that for any given fuel compositions of H-2/CH4, there is an optimum equivalence ratio at which the pollutant emissions (CO and NOx) from the combustor are minimal. Zero CO and 5ppm NOx emissions were observed at the optimal equivalence ratio of 0.45 for a fuel mixture containing 30% H-2. The present study provides a basis for ultra-lean combustion toward achieving zero emissions from a fuel-flexible combustor. Copyright (c) 2016 John Wiley & Sons, Ltd.