The chemical species composition of a vitiated oxidizer stream can significantly affect the combustion processes that occur in many propulsion and power generation systems. Experiments were performed to investigate the chemical kinetic effects of vitiation on ignition and flame propagation of hydrocarbon fuels using propane. Atmospheric-pressure flow reactor experiments were performed to investigate the effect of NOx on propane ignition delay time at varying O2 levels (14–21mol%) and varying equivalence ratios (0.5–1.5) with reactor temperatures of 875K and 917K. Laminar flame speed measurements were obtained using a Bunsen burner facility to investigate the effect of CO2 dilution on flame propagation at an inlet temperature of 650K. Experimental and modeling results show that small amounts of NO can significantly reduce the ignition delay time of propane in the low- and intermediate-temperature regimes. For example, 755ppmv NOx in the vitiated stream reduced the ignition delay time of a stoichiometric propane/air mixture by 75% at 875K. Chemical kinetic modeling shows that H-atom abstraction reaction of the fuel molecule by NO2 plays a critical role in promoting ignition in conjunction with reactions between NO and less reactive radicals such as HO2 and CH3O2 at low and intermediate temperatures. Experimental results show that the presence of 10mol% CO2 in the vitiated air reduces the peak laminar flame speed by up to a factor of two. Chemical kinetic effects of CO2 contribute to the reduction in flame speed by suppressing the formation of OH radicals in addition to the lower flame temperature caused by dilution. Overall, the detailed chemical kinetic mechanism developed in the current work predicts the chemical kinetic effects of vitiated species, namely NOx and CO2, on propane combustion reasonably well. Moreover, the reaction kinetic scheme also predicts the negative temperature coefficient (NTC) behavior of propane during low-temperature oxidation.