A novel method based on conversion of chlorinated volatile organic compounds (CVOCs) to chlorine using a new type of column packed with nanometer TiO2 coupled with chemiluminescence (CL) has been developed for determination of them in workplace air. CVOCs are converted to chlorine by nanometer TiO2 at 220 degrees C. The Cl2 that is produced is selectively enriched on the column and subsequently released from the column at 600 degrees C. The Cl2 that is released is determined using a postcolumn CL detector. The CL intensity was linear with CCl4 in the range of 0.1-380 ppm, and the detection limit was 40 ppb (S/N = 3). Higher sensitivity could be acquired by using a larger volume of enrichment A similar procedure could be used for the determination of other CVOCs. CL intensities of CH2Cl2, CHCl3, and CCl4 at the same concentration increased in the order CH2Cl2 < CHCl3 < CCl4. The method has been successfully applied to the determination of CCl4 in workplace air, where 0.15-150 ppm CCl4 would be detected. The possible mechanism for the long lifetime of the column packed with nanometer TiO2 was tested using Raman spectrometer, X-ray powder diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy. The results showed that the column packed with nanometer TiO2 could be operated in the reversible mode for determination of CVOCs under the present conditions. The method would be potentially applied to the analysis of other chlorinated compounds in environment, such as persistent organic pollutants.