The chromatograms obtained from the gas chromatography‐electron ionization mass spectrometric (GC‐EI‐MS) analysis of extracts containing G‐nerve agents in the presence of diesel, gasoline, etc., are dominated by hydrocarbon backgrounds that “mask” the G‐nerve agents, leading to severe difficulties in identification. This paper presents a practical solution for this challenge by transferring the G‐nerve agents from the organic phase into the aqueous phase using liquid‐liquid extraction (LLE), followed by derivatization with 2‐[(dimethylamino)methyl]phenol (2‐DMAMP), allowing ultrasensitive LC‐ESI‐MS/MS analysis of the G‐derivatives. The proposed approach enables rapid identification of trace amounts of G‐nerve agents with limits of identification (LOIs) at the pg/mL scale.