Ignition and combustion behavior in the second stage of a sequential combustor are investigated numerically at atmospheric pressure for pure CH 4 fueling and for a CH 4 /H 2 fuel blend in 24:1 mass ratio using Large Eddy Simulation (LES). Pure CH 4 fueling results in a turbulent propagating flame anchored by the hot gas recirculation zone developed near the inlet of the sequential combustion chamber. Conversely, CH 4 /H 2 fueling results in a drastic change of the combustion process, with multiple auto-ignition kernels produced upstream of the main flame brush. Chemical Explosive Mode Analysis indicates that, when H 2 is added, flame stabilization in the combustion chamber is strongly supported by auto-ignition chemistry. The analysis of fuel decomposition pathways highlights that radicals advected from the first stage flame, in particular OH, induce a rapid fuel decomposition and cause the reactivity enhancement that leads to auto-ignition upstream of the sequential flame. This behavior is promoted by the relatively large mass fraction of OH radicals found in the flow reaching the second stage, which is approximately one order of magnitude greater than it would be at chemical equilibrium. The importance of the out-of-equilibrium vitiated air on the ignition behavior is proven via an additional LES that features weak auto-ignition kernel formation when equilibrium is artificially imposed. It is concluded, therefore, that parameters affecting the relaxation towards chemical equilibrium of the vitiated flow can have an important influence on the operability of sequential combustors fueled with varying fractions of H 2 blending.