A systematic approach for the identification and quantification of organic volatile impurities (OVIs) in pharmaceutical excipients is described. Analytical procedures utilizing static headspace capillary gas chromatography coupled with flame-ionization and MS detection techniques were developed for the analysis of toxic ICH class 1 solvents and US Pharmacopeia OVIs at sub-ppm levels, and commonly used organic solvents in a wide range of concentrations. Chromatographic conditions and headspace parameters for the methods were optimized for separation, sensitivity, and speed. The proposed methodologies were demonstrated to be selective, accurate, and reproducible, and were successfully applied to the rapid screening of OVIs in typical excipients.