The applicability of a central-rotatable composite design to the optimization of the direct analysis of trace amounts components by using a programmed temperature vaporizer (PTV) operated in the solvent split mode is evaluated. The influence of several variables affecting the introduction of large volume sampling is studied (e.g., injected volume, solvent elimination flow, and the PTV initial temperature). The factors levels at which the measured responses attain the most favorable values, as well as the sensitivity and the accuracy achievable in the gas chromatographic analysis of volatile compounds without demanding the extraction and external concentration of the sample, are investigated. Data concerning the precision of the analysis are also included.