A procedure for detection and quantification of free codeine, free morphine, and 6-acetylmorphine in urine is presented. The analytes were extracted at neutral pH by solid-phase extraction prior to derivatization to their trifluoroacetyl derivatives. The derivatized extracts were analyzed by gas chromatography/mass spectrometry in the electron impact mode. Confirmation of the analytes was accomplished by comparing the ion abundance ratios of the analytes to those of a previously analyzed standard. The qualitative ion abundance ratios were required to be within 20% of those of the standard for acceptance. Quantification was based on the tri-deuterated analogs of the analytes. Linearity was obtained in the range of 10 to 1000 ng/mL, with correlation coefficients of all analytes exceeding 0.999. Percent recoveries were 90% for codeine, 88% for morphine, and 85% for 6-acetylmorphine. No hydrolysis of 6-acetylmorphine occurs during the extraction procedure. The authors also studied the stability of 6-acetylmorphine at various storage conditions of pH, temperature, and chemical preservation. 6-Acetylmorphine was found to be stable for 12 weeks when stored at -17 degrees C.