Objective To establish a method for directly determining RRR-α-tocopherol in milk powder by chiral liquid chromatog.Methods The samples were saponified with potassium hydroxide and extracted with petroleum ether-iso-Pr ether.DAICEL Chiralcel OD-3(2.1 mmx150 mm, 3 μm) was directly separated on a small particle size cellulose derivative chiral column, and isocratic elution was performed using absolute ethanol-n-hexane(5:995, V:V)(A) and triethylamine-n-hexane(5:995, V:V)(B)(A:B=10:90) as the mobile phases, with the flow rate of 0.2 mL/min, the column temperature of 30 °C, the detection wavelength of 294 nm, and the quantification by external standard method.Results The resolutions of RRR-α-tocopherol and other α-tocopherol isomers were greater than 1.2.The linearities were good within the range of 0.5-50 μg/mL, with the correlation coefficient greater than 0.999.The limit of detection was 0.20 mg/100 g, and the limit of quantitation was 0.60 mg/100 g.The recoveries after standard addition were 95.0%-109.4%, and the relative standard deviation was 2.7%.Conclusion This method is rapid, accurate and sensitive, and is suitable for the determination of RRR-α-tocopherol in milk powder.