In this study, alkali impregnated filter sampling method was considered for VFAs in ambient air. When KOH concentration was 0.5 N and sampling flow velocity was 5~10 L/min the sampling efficiency was higher than 90 percent. More than 3 minute shaking make the sampled filter to be suspended in the 22.3 mL Vial. Alkali impregnated filter sampling method showed more than 4 times higher response compared to alkali solution sampling method, when the sample was analysed by headspace-gas chromatography. Five kinds of volatile fatty acids (propionic acid, i-butyric acid, n-butyric acid, i-valeric acid, valeric acid) were detected within 1.0~9.8 ppbv in the cow shed by alkali impregnated filter method and headspace gas chromatography. The alkali impregnated filter method was the most suitable sampling method for ambient volatile fatty acids with headspace gas chromatography analysis.