In recent years, electronic cigarettes (e-cigs) have gained popularity worldwide. Several methods of sample preparation for metabolomics have been reported. However, the analysis of e-cigs by using in vitro/in vivo/clinical samples varies from sample to sample according to the instrument used. Experimental records suggest that exposure to e-liquid may be deleterious to cells in vitro and to animals and humans in vivo. Similarly, different platforms, such as liquid chromatography-mass spectrometry (LCMS), nuclear magnetic resonance (NMR), and capillary electrophoresis (CE), have been employed for analyzing e-cig sample matrices, each of which has specific sample preparation procedures and data analysis techniques. Furthermore, potential biomarkers indicating the early pathogenesis of particular e-cig-associated diseases have been discovered. This research provides an overview of the different technologies used in studying metabolomics in relation to e-cigs. This study highlights how different studies can obtain reliable results by utilizing available software and databases.