The optimal extraction conditions of rapeseed cake oil using subcritical R134a/butane were established by response surface methodology. The quality of subcritical R134a/butane extraction oil (SRBEO) was compared with supercritical CO₂ extraction oil (SCO₂EO) and hexane extraction oil (HXEO). The results showed the highest extraction yield obtained by subcritical R134a/butane in the condition of R134a‐butane ratio of 1.5 kg/kg, at 45°C for 50 min. Compared with SCO₂EO and HXEO, the extraction yield and β‐carotene content of SRBEO (87.76%, 357.21 μg/100g) were the highest. The content of phospholipids and canolol in SRBEO (3.01 mg/g, 118.51 mg/100 g) was higher than SCO₂EO (not detected, 95.82 mg/100 g) and less than HXEO (25.78 mg/g, 131.85 mg/100 g). The tocopherols in SRBEO were equivalent to SCO₂EO but phytosterol content of SRBEO (560.19 mg/100 g) was less than SCO₂EO (591.40 mg/100 g). For fatty acids, the three extraction oils had slight difference. Thus, subcritical R134a/butane extraction appeared to be feasible for rapeseed cake oil extraction.