In the context of sustainable development and green engineering, this study investigates and compares environmentally friendly extraction techniques for obtaining essential oils from Origanum and Mentha species. Essential oils were extracted using hydrodistillation (HD), supercritical CO₂ extraction (SC-CO₂), ultrasound assisted extraction (UAE), and headspace solid phase microextraction (HS-SPME), employing “captured” solvents of different polarity (hexane and toluene). Chemical characterization was performed using GC-FID for quantitative analysis and GC-MS for compound identification. The results demonstrated that extraction technique significantly affects both qualitative and quantitative profiles, with 30–120 compounds identified depending on the method. In Mentha spp., oxygenated monoterpenes dominated, particularly menthone (up to 42.6%) and menthol (up to 38.5%), with SC-CO₂ providing the highest selectivity and recovery. In contrast, UAE extracts were enriched in monocyclic monoterpenes such as α-phellandrene (up to 42.18%) and limonene (up to 25.29%). For Origanum spp., thymol was the main compound, reaching 83.9% in SC-CO₂ extracts, compared to 63.57% in HD and 53.15% in UAE. HS-SPME predominantly captured highly volatile hydrocarbons, including α-pinene (up to 29.06%), reflecting its suitability for aroma profiling rather than total extraction. Solvent polarity, which was used as “captured solvent, further influenced extraction efficiency, with hexane favoring non-polar hydrocarbons and toluene slightly enhancing oxygenated compounds. In conclusion, SC-CO₂ extraction proved to be the most effective and selective method, ensuring high yields and preservation of thermolabile bioactive compounds in both plant species. UAE represents a rapid and energy efficient alternative for hydrocarbon rich fractions, while HS-SPME is optimal for volatile profiling. These findings highlight the critical role of method selection in optimizing extraction strategies tailored to specific phytochemical targets and industrial applications.