This present study was designed to evaluate the performances of five alternative solvents (alcohols: ethanol, isopropanol and terpenes:ρ-limonene, α-pinene, p-cymene) compared to η-hexane in rapeseed oil extraction. The extracted oils were quantitatively and qualitatively analyzed to compare the solvents’ performances in terms of kinetics, fatty acid compositions, lipid yields, and classes. Moreover, micronutrients in extracted oils were also respectively quantified by high-performance liquid chromatography (HPLC) and gas chromatography (GC). In addition, the interactions between alternative solvents and rapeseed oil have been theoretically studied with the Hansen solubility methodology to get a better comprehension of dissolving mechanisms. The results indicated that pcymene could be the most promising solvent for n-hexane substitution with higher lipid yield and good selectivity, despite the micronutrient contents were relatively low.