Determination of perfluorocarboxylic acids (PFCAs) by gas chromatography (GC) has been undertaken since 1980. However, only small number of studies can be found in the literature due to the major drawbacks associated with the GC determination of PFCAs such as high detection limits, a small range of analytes, long analysis time, and laborious derivatization prior to chromatographic separation. Liquid chromatography-tandem mass spectrometry (LC-MS(2)) can overcome these limitations of GC, and therefore has become the method of choice for the determination of PFCAs since 2001. Nevertheless, GC as a low-cost and commonly available analytical technique should not be ignored because of its inherent advantage over LC to identify PFCA isomers in environmental and biological matrices owing to its high-resolution power. In addition, GC provides an opportunity to crosscheck LC-MS(2) results that are often suspicious due to background contamination. This tutorial provides an overview of GC methods that have been used for the determination of PFCAs after derivatization. Moreover, performance characteristics of GC-MS are compared with that of LC-MS(2). PFCAs in aqueous samples were determined by both analytical techniques, and two sets of measurements were compared using the Bland-Altman plot. For both methods, reasons for false-positive and false-negative results (overestimation and underestimation of the PFCA concentration, respectively) are discussed, and accordingly some advice is offered on how to avoid erroneous results. Finally, major applications of GC and its future perspectives for the determination of PFCAs are discussed.