In order to investigate the exhaust structure and secondary oxidation of unburned hydrocarbon (HC) in the exhaust port, concentrations of individual HC species were measured in exhaust process, the degree of oxidation were obtained. Using a solenoid-driven fast sampling system on single-cylinder research engine fueled with 94% propane, the profiles of unburned hydrocarbons (HCs) and non-fuel HCs with a propane fueled engine were obtained from several locations in the exhaust port during the exhaust process. The sampled gases were analyzed using a gas chromatography of HC species with 4 or lesser carbon atoms. The change of total HC concentration and HC fractions of major components through the exhaust port were discussed. The results showed that non-uniform distribution of HC concentration existed around the exhaust valve and changed with time, and that the exhaust gas exhibited nearly uniform concentration profile at port exit, which was due to mixing and oxidation. Also it could be known that bulk gas with relatively high HC concentration came out through the bottom of the exhaust valve. To estimate the mass-based degree of HC oxidation in the exhaust port from measured HC concentrations, a 3-zone diagnostic cycle simulation and plug flow modeling were used. The degree of oxidation ranged between 26 % and 36 % corresponding to the engine operation conditions