Hydrogen-blending effects in flame structure and NO emission behaviour are numerically studied with detailed chemistry in methane air counterflow diffusion flames. The composition of fuel is systematically changed from pure methane to the blending fuel of methane-hydrogen through H-2 molar addition up to 30%, Flame structure, which can be described representatively as a fuel consumption layer and a H-2-CO consumption layer, is shown to be changed considerably in hydrogen-blending methane flames, compared to pure methane flames. The differences are displayed through maximum flame temperature, the overlap of fuel and oxygen, and the behaviours of the production rates of major species. Hydrogen-blending into hydrocarbon fuel can be a promising technology to reduce both the CO and CO2 emissions supposing that NO, emission should be reduced through some technologies in industrial burners. These drastic changes of flame structure affect NO emission behaviour considerably. The changes of thermal NO and prompt NO are also provided according to hydrogen-blending. Importantly contributing reaction steps to prompt NO are addressed in pure methane and hydrogen-blending methane flames. Copyright (c) 2006 John Wiley & Sons, Ltd.