Sucralose is a high intensity, non-nutritive sweetener, which is approximately 600 times sweeter than sucrose. The analysis of this sweetener and similar carbohydrates is challenging, due to both the difficulty of detection as well as the need to separate numerous very similar structures. Capillary Electrochromatography (CEC) was used to analyze sucralose and related carbohydrate compounds. Separation of sucralose and several very similar compounds was achieved by CEC with a C18-silica packing, and low organic content mobile phases. Effects of mobile phase composition on the separation of these compounds are discussed.