In this study, the experimental feasibility of alkali absorption method, recommended for the analysis of volatile fatty acids (VFA), was evaluated by considering the vaporization efficiency in relation to Henry’s law. Many experimental steps involved in the analysis such as absorption of VFA into the solution (as sorbent), extraction of absorbed VFA from solution, and SPME analysis of extracted vapor are all prone to biases. The extent of bias involved in the extraction stage is estimated under the simulated conditions of active purging at two temperature conditions of 25 and 90℃. The results of computation based on this simulated condition indicated that recovery rate of VFA from absorbed solution can be 1.1% and 30.2% after 1 hour of purging, respectively. As this low recovery rate is directly associated with low sensitivity and poor reproducibility, this official testing method is prone to various sources of experimental biases. Because of these limitations involved in VFA analysis, this official method cannot be used reliably to quantify the VFA in ambient air samples. Consequently, it is desirable to replace this method with the other verified method with more confidence such as the combined application of sorbent tube and thermal desorption.