The demand for more suitable eco-friendly extraction processes has grown over the last few decades and driven research to develop efficient extraction processes with low energy consumption and low costs, but always assuring the quality of the volatile oils (VOs). The present study estimated the kinetic extraction and energy consumption of simultaneous hydro- and steam-distillation (SHSD), and SHSD assisted by carbon dioxide (SHSDACD), using an adopted modelling approach. The two isolation methods influenced the VOs yield, chemical composition and biological activities, namely, antioxidant, anti-glucosidase, anti-acetylcholinesterase and anti-inflammatory properties. SHSDACD provided higher VOs yields than the SHSD at a shorter extraction time: 2.8% at 30 min vs. 2.0% at 120 min, respectively, for Rosmarinus officinalis, 1.5% at 28 min vs. 1.2% at 100 min, respectively, for Lavandula angustifolia, and 1.7% at 20 min vs. 1.6% at 60 min, respectively, for Origanum compactum. The first order and sigmoid model fitted to SHSD and SHSDACD, respectively, with R2 value at 96% and with mean square error (MSE) < 5%, where the k distillation rate constant of SHSDACD was fivefold higher and the energy consumption 10 times lower than the SHSD. The rosemary SHSD and SHSDACD VOs chemical composition were similar and dominated by 1,8-cineole (50% and 48%, respectively), and camphor (15% and 12%, respectively). However, the lavender and oregano SHSDACD VOs were richer in linalyl acetate and carvacrol, respectively, than the SHSD VOs. The SHSDACD VOs generally showed better capacity for scavenging the nitric oxide and superoxide anions free radicals as well as for inhibiting α-glucosidase, acetylcholinesterase, and lipoxygenase.