The formation process of hydrocarbon emissions was investigated in SI engine. The time- resolved concentrations of hydrocarbon emissions were measured using a high gas sampling valve and a gas chromatography. The gas was sampled at exhaust port, or the position of spark plug, or the wall of combustion chamber. The experiments were conducted using the Alpha engine of Hyundai Motor Company. The fuel used was methanol or propane. It was found that the effect of the quenching layer of combustion chamber wall on hydrocarbon emissions was not significant. The increasing rate of hydrocarbon concentration at combustion chamber wall near crevice and oil layer after flame was reached was much higher than that at the position of spark plug. The hydrocarbon concentrations at exhaust port had two peak values just after opening exhaust valve and just before closing it.