In this work, new pH-sensitive hexagonal boron nitride–polysaccharides nanosystems were produced using sol–gel method. These hybrid sol–gel systems include β-cyclodextrin (β-CD), dextrin (Dex), shellac wax (Wax), and polyethylene glycol which were synthesized with hexagonal boron nitride (h-BN) by coupling of triethyl orthosilicate and donepezil. The release studies of DNP from each sol–gel systems were studied using buffers at various pH levels such as 2.2, 4.0, 6.0, 7.4, and 8.6. The release percentages of the drug were calculated by regression equations of the DNP which has maximum fluorescence intensity at 325 and 387 nm excitation and emission wavelengths. These new sol–gel hexagonal boron nitride systems were characterized by Fourier transform infrared spectroscopy, transmission electron microscopy, and scanning electron microscopy analysis. According to the results. The sol–gel systems with polysaccharide-based dextrin (h-BN–Dex) and shellac wax (h-BN–Wax) were more available at a pH levels of 6, 7.4, and 8.6 for the release of DNP. Graphical abstract: (Figure presented.).