A simple, rapid, accurate, precise headspace gas chromatographic (HS-GC) method was developed and validated for simultaneous quantitation of organic volatile impurities (residual solvents) in technical-grade active ingredients (TGAIs) of pesticides and agrochemicals. The HS-GC method utilizes conventional capillary columns. The HS-GC operating conditions were optimized, and 18 organic volatile impurities were efficiently separated. The versatility of the method was confirmed in terms of validation characteristics of specificity, limit of quantitation, linearity, accuracy, and precision. The proposed method was successfully applied to the analysis of pesticide and agrochemical TGAIs.