For the analysis of trace organic pollutants in environmental samples using a gas chromatographic (GC) instrument, large-volume injection using the programmable temperature vaporization (PTV) technique has many advantages over the traditional split/splitless injection. By increasing the injection volume from 1 or 2 microL with a split/splitless inlet to 60 microL or higher with the PTV inlet, analytical sensitivity is greatly enhanced for analytes with low concentrations. Results obtained from optimization of instrument operational parameters for analyzing polycyclic aromatic hydrocarbons (PAHs) are reported in this paper. The laboratory method detection limits for 16 PAHs and six deuterated PAH surrogates were determined using seven replicate spike samples. The initial temperature of the inlet was found to be critical in determining the analytical sensitivity of PAHs with two or three rings due to loss of these relatively highly volatile compounds during solvent vaporization. For most PAHs, the response of the mass spectrometry detector increased proportionally as the total injected volume was increased up to 150 microL. Significant interference from rubber material of the sample vial septa was observed.