A coupled capillary column system was developed for the qualitative and quantitative determination of melamine with isotope internal standard in dairy products by gas chromatography/mass spectrometry (GC/MS) without derivatization. A 30 m of DB-5 ms ((5%-phenyl)-methylpolysiloxane, 0.25 mm i.d., 0.25 microm df) coupled with a 1.5 m of Innowax (polyethylene glycol, 0.32 mm i.d., 0.25 microm df) by a quartz capillary column connector was introduced as separation column. Three advantages were discussed for the coupled system. The sample was fortified with a ring-labeled (13)C(3)(15)N(3)-melamine as an isotope internal standard and extracted by 1% of trichloroacetic acid aqueous solution. 2.2% of lead acetate solution was then added to deposit protein in the sample matrix. After purification by cation exchange cartridge, the sample solution was directly injected and detected by GC/MS. A six-point calibration curve ranging from 0.05 to 2 mg kg(-1) of melamine in sample was used to establish instrument response. The recovery was 93.9-102% with relative standard deviation from 3.1 to 8.7% when isotope internal standard used. The calculated method detection limit was 0.01 mg kg(-1).