Sucralose is an increasingly popular artificial sweetener and has been found in the environment in groundwater, surface water, and wastewater treatment plant effluent. Its chemical properties make it strongly recalcitrant in the environment and it has been used as a conservative tracer of human wastewater in recent years. Most current methods of sucralose analysis use high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) instrumentation. In this study, we describe an analytical method using silylation derivatization and gas chromatography mass spectrometry (GC-MS) for the quantification of sucralose in groundwater samples. This method employs a deuterium-labeled internal standard to account for reaction and sample processing imprecision. The deuterated internal standard as well as experiments using negative ion chemical ionization gas chromatography-mass spectrometry strongly indicate that sucralose is derivatized at all five hydroxyl positions with trimethyl silyl groups. A previously developed GC-MS method with derivatization of sucralose in environmental samples did not employ an internal standard for quantification. As such, this method represents a more robust methodological approach for sucralose quantification in environmental samples. The method detection limit based on a set of 15 method blanks was calculated to be 21.8 ng L⁻¹, which is competitive with most methods in the published literature and sufficient to detect sucralose in water with ∼0.1% wastewater contribution. The method was applied to 37 groundwater samples from drinking water wells in California's Central Valley, in which five samples (13.5%) were found to contain sucralose at concentrations greater than the 21.8 ng L⁻¹ detection limit.