OBJECTIVE: To establish the method for the determination of 25-hydroxyvitamin D [25(OH)D] in human plasma, and apply it in the clinic. METHODS: After liquid-liquid extraction, UPLC-MS/MS method was used to determine plasma sample. Using deuteron-25(OH)D3 as internal standard, the determination was performed on Zorbax Eclipse Plus C18 column with mobile phase consisted of water (containing 0.1% formic acid)-methanol (containing 0.1% formic acid) in gradient mode at flow rate of 0.35 ml/min, and the column temperature was 30 ℃. By ESI, positive ion scanning was conducted in MRM mode; the monitoring transition ion-pair was m/z 413.2→395.2 for 25(OH)D2, m/z 401.2→383.2 for 25(OH)D3 and m/z 404.3→368.2 for internal standard. RESULTS: The linear range of 25(OH)D2 and 25(OH)D3 were both 2-80 ng/ml (r=0.998 0 and 0.999 9, n=3); the limit of quantitation was 2 ng/ml. RSDs of inter-day and intra-day were 0.78%-9.42%, and relative deviation were -2.90%-1.95%, respectively. Average plasma concentration of 25(OH)D in 78 health volunteers and 98 tuberculosis patients were(21.53±6.33)and(8.84±4.05)ng/ml, with statistical significance (P<0.01). CONCLUSIONS: The method is accurate, reliable and sensitive. It is suitable for quantitative analysis and pharmacokinetic study of 25(OH)D in human plasma.