Abstract A new capillary electrophoresis method dedicated to the analysis of neutral underivatized carbohydrates was recently developed by our group. It involved a background electrolyte composed of 98mM NaOH and 120mM NaCl, and direct UV detection via the formation of an absorbing intermediate in the detection window by photooxidation. This article focuses on the validation of this method for the determination of fructose, glucose, lactose, and sucrose in forensic, pharmaceutical, and beverage samples. Intermediate precisions were about 2.3% for normalized corrected peak areas and 1.8% for normalized migration times using naphthalenesulfonate as internal standard. Limits of detection varying from 5μM for sucrose and lactose to 7μM for glucose and 10μM for fructose were obtained. Potential matrix effects were statistically studied for soil, cloth, plastic, cotton, red wine, and with simulated iron, calcium, and sucrose-based matrices, containing various inorganic anions and cations, sometimes at high levels. No significant matrix effect was observed. Finally, analyses of real post-explosion residues, smoke device, cough syrup, red wine, and apple juice were successfully performed.