This study aimed to enhance gas chromatography (GC) methods for the quantification of nine saccharides in processed food products. We developed an optimized extraction protocol using heat-based pre-treatment and employed an HP-5 column for efficient separation, achieving a resolution of 2.11 between mannose and galactose. The method was validated with limits of detection (LOD) and quantification (LOQ) ranging from 0.01 to 0.07 and 0.03–0.10 mg/100 g, respectively. Precision and accuracy were confirmed through analyses of lactose-free milk powder and mixed fruit juice samples. Our approach yielded the highest recorded levels of saccharides in lactose-free milk powder and was successfully applied to quantify free sugars in various commercial food products. This robust GC-based method offers superior resolution and efficient extraction, providing a valuable tool for accurate and reliable characterization of mono- and di-saccharides in diverse food matrices.