Initiator could accelerate the rate of hydrocarbon pyrolysis and reduce the required material temperatures for a hypersonic aircraft heat exchanger(reactor. Nitroalkanes were proposed as the effective initiator because of the lower C-N bond dissociation energy. In order to investigate the initiation mechanism of nitroallones on hydrocarbon pyrolysis, the pyrolysis of n-decane, nitromethane and their binary mixture were carried out at 30, 150 and 760 Torr in a flow reactor with synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS). The identified and quantified pyrolysis species include C-1-C-2 alkanes, C-2-C-10 alkenes, C-3-C-6 dialkenes, C-2-C-3 alkynes, nitrogen oxides such as NO and NO2, benzene, and radicals including CH3, C3H3, and C3H3, which shed light on the mechanism of n-decane and nitromethane pyrolysis, as well as the interactions of these two fuels. The experimental results indicate that the addition of nitromethane decreases the initial decomposition temperature of n-decane, and a stronger promotion effect could be obtained as the experimental pressure increases. The distributions of alkanes, alkenes, dialkenes, alkynes and benzene are also influenced by the addition of nitromethane. A detailed kinetic model with 266 species and 1648 reactions was developed and validated against the mole fraction profiles of reactants, major products and important intermediates during the pyrolysis of each fuel and their binary mixture. The satisfactory model prediction to the experimental measurements permits the analysis of the kinetic effect of nitromethane initiation on the pyrolysis of n-decane. So that, the increase of the conversion rate at a lower temperature, the selectivity of decomposition products, and reduction of benzene formation are better understood. (C) 2015 The Combustion Institute. Published by Elsevier Inc. All rights reserved.