This work describes the development and application of two optimized electrolytes: 15 mmol/L sorbate, 0.2 mmol/L CTAB, and 35 mmol/L sodium hydroxide for the determination of fructose, glucose, maltose, maltotriose, and sucrose in cereals and 15 mmol/L sorbate, 0.3 mmol/L CTAB, and 55 mmol/L sodium hydroxide for the determination of fructose, glucose, galactose, lactose, and sucrose in dairy products. Both methods were validated with respect to linearity, limits of detection (using both signal-to-noise ratio and the Eurachem approach), recovery tests, and intra- and inter-day precision exhibiting adequate performance. Additionally, statistically similar results were obtained in a comparative study of extraction procedures for carbohydrates using the AOAC protocol, ultrasound extraction, magnetic stirring, and sample dissolution.