Supercritical fluid extraction with a rectification process was developed with a view to separating nobiletin from citrus peels. With CO2-ethanol extraction-rectification systems, nobiletin with carotenoids were recovered from top of the rectification tower, while chlorophylls were recovered from the bottom of the tower. With CO2-ethanol-water systems, nobiletin was recovered from top of the rectification tower, while carotenoids and chlorophylls were recovered from bottom of the tower and separated from each other. Rectification conditions for separation of nobiletin from extracts were optimized by taking into consideration the phase separation of CO2-ethanol-water systems.