We improved the detection sensitivity of neutral and amino monosaccharides labeled with 2-aminoacridone by a factor of 19.6-48.7 and 44.4-65.9, respectively, with no deterioration in separation resolution, using a pH discontinuous solution system instead of the conventional solution system. The pH discontinuous solution system is simple, using only a borate solution at pH 6.0 as a sample solution and a Tris-borate solution at pH 9.3 as a separation solution, enabling an enhancement of the sensitivity by monosaccharide stacking. This technique is fully compatible with conventional microchip electrophoresis, thereby allowing us to develop efficient tools for highly sensitive and resolved detection of monosaccharides.