The current study aimed at evaluation of the dissolving power of various vegetable oils in both theoretical and experimental way for the extraction of volatile aroma compounds (VACs) from basil. The solubility of six main VACs from basil in ten vegetable oils was firstly investigated through a theoretical modeling of their Hansen solubility parameters (HSP), followed by real experimental extractions using vegetable oils as solvents instead of petroleum-based solvents such as dichloromethane. Furthermore, multivariate statistical analyses were performed to partition vegetable oils into clusters referring to their dissolving power of VACs, which could be quantified by gas chromatographyemass spectroscopy (GCeMS) coupling to the headspace solid phase micro-extraction (HS-SPME). The results indicated that the solubility of VACs in enriched vegetable oils was significantly different (p < 0.05). Vegetable oils has theoretically and experimentally proved their potential to be alternative solvents for further application in green extraction of natural products, in which sunflower oil gave the best performance.