The effect of NO and NH_3 doping on high temperature reaction (HTR) was examined. Numerical analysis based on detailed chemical kinetic reaction model was conducted for methane/air homogeneous charge compression ignition (HCCI) process as the representative of the HTR. The calculation results were verified experimentally using a single cylinder HCCI test engine. From engine experiment, it was shown that a small amount of NO and NH3 strongly promoted methane oxidation, meanwhile a larger amount suppressed the promotion effect. The detailed reaction mechanism on the effect of NO and NH_3 doping was discussed based on elementary reaction analysis.