The aim of this research was to investigate the mechanism causing autoignition and the effect of exhaust gas recirculation (EGR) on combustion by detecting the behavior of the OH radical and other excited molecules present in the flame in a spark ignition engine. The test equipment used was a 2-cycle engine equipped with a Schnürle scavenging system. Using emission spectroscopy, the behavior of the OH radical was measured at four locations in the end zone of the combustion chamber. The OH radical plays an important role in the elemental reactions of hydrocarbon fuels. When a certain level of EGR was applied according to the engine operating conditions, the unburned gas became active owing to heat transfer from residual gas near the measurement positions on the exhaust port side and the influence of excited species in the residual gas, and autoignition tended to occur.