AbstractThe on‐line coupling of a liquid‐liquid extraction system with capillary gas chromatography using atomic emission detection (GC‐AED) has been studied. The required large volumes of about 100 μl of an iso‐octane solution can be introduced into the GC‐AED system by using the AED solvent vent and a solvent vapor exit in front of the capillary analytical column. Test solutions containing several pesticides were detected using the carbon, chlorine, nitrogen and sulfur channels. Analyte detectability (in concentration units) was improved significantly and low concentractions of the test compounds could be determined (1–5 ng/ml). Aqueous samples were on‐line extracted and analyzed. The precision of the large‐volume injection itself as well as the total extraction‐GC‐AED system was satisfactory (RSD ofca.2 and 4%, respectively). As a real‐life application, several ground water