There is significant interest in using hydrogen and natural gas for enhancing the performance of diesel engines. We report herein a numerical investigation on the ignition of n-C(7)H(16)/H(2) and n-C(7)H(16)/CH(4) fuel blends. The CHEMKIN 4.1 software is used to model ignition in a closed homogenous reactor under conditions relevant to diesel/HCCI engines. Three reaction mechanisms used are (i) NIST mechanism involving 203 species and 1463 reactions, (ii) Dryer mechanism with 116 species and 754 reactions, and (iii) a reduced mechanism (Chalmers) with 42 species and 168 reactions. The parameters include pressures of 30 atm and 55 atm, equivalence ratios of phi = 0.5, 1.0 and 2.0, temperature range of 800-1400 K, and mole fractions of H(2) or CH(4) in the blend between 0 and 100%. For n-C(7)H(16)/air mixtures, the Chalmers mechanism not only provides closer agreement with measurements compared to the other two mechanisms, but also reproduces the negative temperature coefficient regime. Consequently, this mechanism is used to characterize the effects of H(2) or CH(4) on the ignition of n-C(7)H(16). Results indicate that H(2) or CH(4) addition has a relatively small effect on the ignition of n-C(7)H(16)/air mixtures, while the n-C(7)H(16) addition even in small amount modifies the ignition of H(2)/air and CH(4)/air mixtures significantly. The n-C(7)H(16) addition decreases and increases the ignition delays of H(2)/air mixtures at low and high temperatures, respectively, while its addition to CH(4)/air mixtures decreases ignition delays at all temperatures. The sensitivity analysis indicates that ignition characteristics of these fuel blends are dominated by the pyrolysis/oxidation chemistry of n-heptane, with heptyl (C(7)H(16)-2) and hydoxyl (OH) radicals being the two most important species. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.