We used gas chromatography in conjunction with flame ionization detection to quantitate nine polyols and aldo and keto sugars (as silyl derivatives) in human plasma and cerebrospinal fluid (CSF). Rhamnose, not found in CSF or plasma, was used as an internal standard with a lower limit of quantitation of 0.4 mg/l. CSF polyol and sugar concentrations (mean +/- S.D.) in fourteen healthy subjects (age range 27.1-85.9 years) were: anhydroglucitol, 19.9 +/- 5.3 mg/l; arabitol, 4.8 +/- 0.9 mg/l; erythritol, 2.4 +/- 0.5 mg/l; myoinositol, 28.6 +/- 8.3 mg/l; ribitol, 1.6 +/- 0.1 mg/l; fructose, 25.5 +/- 11.1 mg/l; glucose, 587 +/- 70 mg/l; glucitol, 7.7 +/- 1.5 mg/l; and mannose, 10.6 +/- 2.4 mg/l. The respective plasma concentrations were 30.6 +/- 11.5, less than 0.4, 0.4 +/- 0.2, 6.3 +/- 2.6, less than 0.4, 23.4 +/- 21.4, 897 +/- 214, less than 0.4 and 13.7 +/- 6.3 mg/l. Polyol CSF-to-plasma concentration ratios greater than 2 were observed for myoinositol, erythritol, arabitol, glucitol and ribitol, indicative of active accumulation or synthesis of these polyols within the central nervous system.