Hydrogen (H2) is known to be the fastest fuel to ignite among all practical combustion fuels. In this study, for the first time, longer ignition delay times (IDTs) for the H2 and H2 blended CH4 mixtures were measured compared to those for pure CH4. This work investigates the ignition characteristics of H2, CH4, and 50% CH4/50% H2 mixtures using a rapid compression machine at pressures ranging from 20 to 50 bar and at equivalence ratios (φ) from 0.5 to 2.0 in air in the temperature range 858–1080 K. The experimental IDTs are simulated using a newly updated kinetic mechanism, NUIGMech1.3, and good agreement is observed. At lower temperatures the IDTs of H2, CH4, and the 50% CH4/50% H2 mixtures are similar to one another, and the IDTs of the 50% CH4/50% H2 mixtures are longer than those for pure CH4 at temperatures below 930 K. At temperatures below 890–925 K, depending on the operating pressure and equivalence ratio, the hydrogen mixtures are the slowest to ignite, with IDTs being 2.5 times longer than those recorded for CH4 at a pressure of 40 bar at 890 K for φ = 1.0, and at 875 K for φ = 2.0. At low temperatures alkyl (Ṙ = ĊH3 and Ḣ) radicals add to O2 producing RȮ2 radicals, which then react with HȮ2 radicals forming ROOH (H2O2 and CH3OOH) and O2. For H2, the self-recombination of HȮ2 radicals leads to chain propagation which inhibits reactivity, whereas for CH4, the reaction between RȮ2 (CH3OȮ) and HȮ2 leads to chain branching, increasing reactivity. Furthermore, CH3OOH decomposes more easily to produce CH3Ȯ and ȮH radicals than does H2O2 to produce two ȮH radicals. Thus, mixtures containing higher H2 concentrations are slower to ignite compared to those with higher CH4 concentrations at low temperatures.