Display omitted •Commercial biopesticides characterization by targeted and untargeted analyses.•A home-made database was built by LC and GC-HRMS methodologies.•17 target and 101 untargeted compounds were detected in the tested samples.•In addition to natural compounds, BHT or diisobutyl phthalate were detected. 15 commercial biopesticides (CBs), based on vegetable extracts and oils, were characterized. Ultra-high-performance liquid chromatography (UHPLC) and gas chromatography (GC) coupled to a hybrid high-resolution mass spectrometry (HRMS) analyser, such as quadrupole (Q)-Orbitrap, were used. Both targeted and untargeted (suspect and unknown modes) analyses were carried out. For the targeted analysis, a database was built, encompassing volatile and non-volatile compounds commonly found in vegetable extracts and oils. This database comprised 27 LC-amenable compounds and 31 GC-amenable compounds. 17 targeted compounds were quantified, and 101 compounds were tentatively identified by untargeted analysis. CBs based on essential oils, such as orange oil or cinnamon extract contained the highest number of detected compounds. Monoterpenes (limonene or linalool), and sesquiterpenes (δ-cadinene or γ-elemene) were mainly found. Moreover, some co-formulants such as dibutyl phthalate or butylated hydroxytoluene (BHT) were also detected. The concentration of targeted natural compounds ranged from 2 mg/L (linalool) to 450 g/L (trans-cinnamaldehyde).