To facilitate urine sample preparation prior to head-space gas-chromatographic (HS-GC) analysis. Urine samples containing one of the five solvents (acetone, methanol, methyl ethyl ketone, methyl isobutyl ketone and toluene) at the levels of biological exposure limits were aspirated into a vacuum tube via holder, a device commercially available for venous blood collection (the vacuum tube method). The urine sample, 5 ml, was quantitatively transferred to a 20-ml head-space vial prior to HS-GC analysis. The loaded tubes were stored at +4°C in dark for up to 3 d. The vacuum tube method facilitated on-site procedures of urine sample preparation for HS-GC with no significant loss of solvents in the sample and no need of skilled hands, whereas on-site sample preparation time was significantly reduced. Furthermore, no loss of solvents was detected during the 3-d storage, irrespective of hydrophilic (acetone) or lipophilic solvent (toluene). In a pilot application, high performance of the vacuum tube method in sealing a sample in an air-tight space succeeded to confirm that no solvent will be lost when sealing is completed within 5 min after urine voiding, and that the allowance time is as long as 30 min in case of toluene in urine. The use of the holder-vacuum tube device not only saves hands for transfer of the sample to air-tight space, but facilitates sample storage prior to HS-GC analysis.