This study assessed the measurement technique of odorous substances using a GC/MOS system with MOS sensor at the detector and the method detection limits were determined for odorous substances such as hydrogen sulfide, acetaldehyde, toluene, m,pxylene, and o-xylene. The portable GC/MOS system was able to separate and measure about 16 out of 22 odorous substances including sulfur compounds, aldehydes, and VOCs. The peak values for hydrogen sulfide, acetaldehyde, toluene, m,p-xylene, and o-xylene showed a nonlinear relationship with concentration and a correlation coefficient of 0.95 or higher was confirmed. The method detection limits for hydrogen sulfide, acetaldehyde, toluene, m.pxylene, and o-xylene using the portable GC/MOS system were determined to be 0.005, 0.023, 0.016, 0.004, and 0.051 ppm, respectively. It is expected that the system can measure odor samples with concentrations of least 50 ppb without additional pretreatment or concentration processes.