DDVP was isolated from white spirits using Solid-Phase Microextraction (SPME) technique, and determined by wide-bore capillary gas chromatography (GC) coupling a flame ionization detector. This method had an excellent linearity among 0.5-12 mg/L. Correlation coefficient and minimum detectable concentration were 0.9983 and 0.05 mg/L respectively. This method enables the extraction, the enrichment and the injection to integrate into a single step, and it was free-solvent in whole process. SPME is an advanced technique for the extraction and analysis of the samples.