Gamma‐aminobutyric acid (GABA), which has attracted much attention as a bioactive ingredient, is used in functional foods. Recently, electronic cigarette (e‐cigarette) products for inhaling vaporized GABA have become commercially available. In this study, we developed a high‐performance liquid chromatography–fluorescence method for detecting GABA derivatized with 4‐(N,N‐dimethylaminosulfonyl)‐7‐fluoro‐2,1,3‐benzoxadiazole (DBD‐F) in cigarette smoke extract (CSE). The vaporized GABA captured in CSE was derivatized with DBD‐F under moderate conditions (80°C, 30 min). After chromatographic separation, the DBD‐GABA derivative was detected at 437 and 558 nm. The calibration curve of GABA ranging from 10 to 20,000 ng/mL showed good linearity (more than 0.999). The limit of detection at a signal‐to‐noise ratio of 3 was 1.1 ng/mL. The method was applied to the detection of GABA in e‐liquid and CSE for two kinds of e‐cigarette products, and the estimated collection efficiency of GABA was approximately 25%. Furthermore, the detection of minor components, such as glutamine, glutamic acid, and arginine, in the e‐liquid proved that the GABA used in the e‐cigarette was prepared by microbial fermentation.