The on‐line coupled LC‐GC technique was applied to the analysis of several metal chelates of N,N‐diethyldithiocarbamic acid. A 10‐port valve interface was used to couple the LC and GC instruments. Conditions during sample transfer into the GC gave fully concurrent solvent evaporation. The chelates investigated were separated with a short apolar fused silica column. LC preseparation was made with cyano or amino phases using a hexane/dichloromethane mixture as eluent. On‐line LC‐GC combination seems to be very suitable for the separation of the metal chelates studied.