The development, optimization and validation of a gas chromatography-mass spectrometry (GC-MS) method for trace levels of methylmethanesulfonate (MMS), ethylmethanesulfonate (EMS), methyl-ptoluenesulfonate (Mp-TS) and ethyl-p-toluenesulfonate (Ep-TS) in Simvastatin was presented. The factors affecting the identification and determination were discussed. A capillary column (30 m  0.25 mm i.d.) coated with 0.25 mm film was used for separation. The calibration curves of four sulfonate esters showed good linearity (R 2 > 0.99) within the range of 0.5-10 mg L À1 . The optimized method proved to be reproducible (%R.S.D.s less than 6%) and suitable for use with external standard quantitation, and also met basic validation requirements.