In the present study, the effects of hydrogen enrichment of methane are investigated numerically from the diffusion flame structure and emissions aspect. Fluent code is utilised as the simulation tool. In the first part of the study, four experiments were conducted using natural gas as fuel. A non-premixed burner and a back-pressure boiler were utilised as the experimental setup. The natural gas fuel consumption rate was changed between 22 Nm(3)/h and 51 Nm(3)/h. After the experimental studies, the numerical simulations were performed. The non-premixed combustion model with the steady laminar flamelet model (SFM) approach was used for the calculations. The methane-air extinction mechanism was utilised for the calculation of the chemical species. The numerical results were verified with the experimental results in terms of the flue gas emissions and flue gas temperature values. In the second part of the study, four different hydrogen-enriched methane combustion cases were simulated using the same methane-air extinction mechanism, which included the hydrogen oxidation mechanism as a sub mechanism. The same energy input (432 kW) was supplied into the boiler for all the studied cases. The obtained results show that the hydrogen addition to methane significantly change the diffusion flame structure in the combustion chamber. The hydrogen-enriched flames become broader and shorter with respect to the pure methane flame. This provides better mixing of the reactants and combustion products in the flame regions due to the use of a back-pressure boiler. In this way, the maximum flame temperature values and thermal NO emissions are reduced in the combustion chamber, when the hydrogen addition ratio is less than 15% by mass. The maximum temperature value is calculated as 2030 K for the case with 15% hydrogen addition ratio by mass, while it is 2050 K for the case without hydrogen enrichment. Therefore, it is determined that the hydrogen-enriched methane combustion in a back-pressure combustion chamber has the potential of reducing both the carbon and thermal NO emissions. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.