AbstractTwo kinds of capillary columns were prepared and tested as the stationary phases of ligand exchange gas chromatographic separation of dialkyl sulfides. The PTFE column wall‐coated with silane‐DTC‐Cu but without the addition of silicone exhibits significantly better selectivity towards dialkyl sulfides than a column wall‐coated with 10% silane‐DTC‐Cu in silicone. With the first column connected to a microsample injection valve and a microsample loop, the quantitative determination of dialkyl sulfides can be performed. The column also shows great promise for the separation of dialkyl sulfide‐hydroca