A number of synthetic cannabinoids have been appearing in the recreational drug market for more than a decade. Recent additions are so‐called semi‐synthetic cannabinoids, and they structurally closely resemble the main psychoactive component of cannabis, Δ9‐tetrahydrocannabinol. Knowledge of new (semi‐)synthetic cannabinoids is essential to help identify them in authentic forensic case samples. Therefore, the aim of the study was to examine two commercially available electronic cigarette liquid products claiming to contain cannabinoids and characterize the structures of the main compounds. The liquid products were analyzed by gas chromatography–mass spectrometry (GC–MS), GC–quadrupole time‐of‐flight mass spectrometry (GC‐QTOF‐MS), and liquid chromatography–high‐resolution mass spectrometry (LC–HRMS). In product A, typical cannabinoids (cannabidiol, cannabigerol, and cannabinol) and terpenes (α‐caryophyllene and β‐caryophyllene) were identified by comparison with reference materials. An unknown peak was isolated by semi‐preparative high‐performance LC, analyzed by nuclear magnetic resonance (NMR) spectroscopy, and identified to be Δ9‐tetrahydrocannabihexol acetate (Δ9‐THCH‐O). To the authors' knowledge, this is the first report of the identification of Δ9‐THCH‐O in commercially available products. Another compound estimated as cannabihexol acetate was also detected. In product B, cannabidiol, cannabinol, α‐caryophyllene, and β‐caryophyllene were identified, while two unknown peaks were estimated as tetrahydrocannabidiol isomers. Despite products A and B being labeled to contain “60% HHCPM” and “80% 10‐OH‐HHC,” respectively, no such compounds were detected. The findings of this study could help detect Δ9‐THCH‐O in case samples and highlight the need to keep monitoring commercial products to identify new drugs, while warning that the package labels cannot be trusted.