Ammonia (NH3) has been recognized as a potential carbon-free synthetic fuel of the near future. To enhance its low reactivity, one practical option is to blend it with hydrogen (H2). In this study, the transient head-on quenching of premixed laminar ammonia/air flames enriched with hydrogen is explored based on numerical simulations using detailed chemistry and the mixture-averaged transport model. In this respect, nine different test cases are studied for blending ratios (the molar ratio of hydrogen to the ammonia/hydrogen mixture) of 0.0, 0.2, and 0.4, equivalence ratios of 0.8, 1.0, and 1.2, wall temperatures of 300, 500, and 750 K, and pressures of 1, 2, and 5 atm. The results reveal that the quenching distance (maximum absolute wall heat flux) decreases (increases) with increasing the blending ratio, the equivalence ratio, the wall temperature, and the pressure. For all the test cases, the quenching Peclet number changes between 1 and 3.5. In addition, the local heat release rate enhancement and the role of radical recombination reactions are highlighted at the time of quenching in the vicinity of the wall. This effect is augmented as the blending ratio, the equivalence ratio, and the wall temperature increase. Furthermore, the results show that the N2 pathway is the dominant pathway in consumption of NO near the wall at the time of quenching, in which R76 (NH2+NO⇔N2+H2O) poses the rate controlling role. In addition, the leading role of R85 (NH+NO⇔N2O+H) in consuming NO and converting it to N2O is highlighted at the time of quenching near the wall. Moreover, the significant roles of molecular diffusion and reaction source terms over convection are discussed for both NO and N2O species transport in the vicinity of the wall.Novelty and significance statement: The significance of this work is that using ammonia and its blends with hydrogen as promising carbon-free fuels for the future has several technical issues/uncertainties, which needs to be addressed fundamentally. One of the relatively unexplored issues in the combustion devices for ammonia/hydrogen/air flames is the head-on quenching phenomenon, which is investigated in detail in this study. The novelty of this work is that, for the first time, (1) the head-on quenching of various ammonia/hydrogen blends is systematically studied numerically, employing detailed chemistry, (2) effect of wall on the heat release rate chemistry is discussed wherein the role of radical recombination reactions is highlighted, and (3) the formation pathways of pollutant emissions (NO and N2O) for such flames are thoroughly investigated in the freely propagating flame scenario and in the vicinity of the wall at the time of quenching.