Deep eutectic solvents (DES) composed of citric acid monohydrate (CAM) as hydrogen bond acceptor (HBA) and alcohol as hydrogen bond donor (HBD) were used for separating bioactive compounds from star anise. This study prepared three propane alcohols-based DES with different hydroxyl (OH) group densities in HBD. FTIR analysis verified the presence of hydrogen bond interactions between HBA and HBD, which strengthened with increasing the OH group densities. Increasing the OH group density in DES exhibited lower water content, but higher thermal stability, higher density, higher viscosity as well as enhanced the water absorption rate. All of the propane alcohols-based DES were miscible in high and semi-polar solvents as well as it also displayed frequency independence characteristics. Moreover, propane alcohols-based DES efficiently extracted bioactive compounds from star anise with high total phenolic and flavonoid contents more than traditional solvents. High bioactive phenolic and flavonoid contents in star anise extracts were the major contributors to potent antioxidant activities of 2,2-diphenyl-1-picrylhydrazyl (DPPH, 84.50 %), azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS, 85.73 %), and ferric ion reducing antioxidant power (FRAP, 3.74 mM FeSO4). Therefore, DES was suggested to be a promising extraction medium for valuable bioactive compounds from natural sources that could be utilized as therapeutic agent for oxidative stress.