Rich and underutilized, pomegranate peel is a powerful source of nutrients with significant concentrations of dietary fibre, antioxidants, vitamins C and E, potassium, and punicalagin, among other bioactive substances. This study investigated the process of extracting bioactive substances from pomegranate peel, an agricultural food waste. Pomegranate peel extractions were carried out under liquid and supercritical conditions using carbon dioxide (CO2), an environmentally acceptable solvent. We also investigated whether ethanol might be used as a cosolvent in tiny amounts of up to 30%. The extracts' antiradical activity, volatile organic chemicals, total polyphenolic levels, and individual polyphenolic profiles were assessed. When 30% ethanol was utilized as a cosolvent in both liquid (at 25 MPa and 30 °C) and supercritical (at 40 MPa and 50 °C) CO2 extraction, the best yields were obtained. Furthermore, the extracts made with liquid CO2 plus 30% ethanol had the highest concentrations of terpenes, specifically limonene, and naringin (36.41) among pomegranate peel extracts. According to ABTS+ and DPPH measurements, this extract type exhibited the highest antiradical activity (32.33–6-3.78 µmolTE g-1). These results indicate that the extraction using a liquid CO2 and ethanol mixture may be a good substitute for conventional solvent extraction, which uses 70% less organic solvent, and yields extracts rich in volatile organic chemicals and with strong antiradical activity.