The conversion of alcohols towards aldehydes in the presence of catalysts by non-oxidative dehydrogenation requires special importance from the perspective of green chemistry. Sodium (Na) super ionic conductor (NASICON)-type hydrogen titanium phosphate sulfate (HTPS; H_1-xTi₂(PO₄)_3-x(SO4)_x, x = 0.5–1) catalysts were synthesized by the sol-gel method, characterized by N₂ gas sorption, X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), NH₃ temperature-programmed desorption (NH₃-TPD), ultraviolet–visible (UV-VIS) spectroscopy, and their catalytic properties were studied for the non-oxidative dehydrogenation of methanol and ethanol. The ethanol is more reactive than methanol, with the conversion for ethanol exceeding 95% as compared to methanol, where the conversion has a maximum value at 55%. The selectivity to formaldehyde is almost 100% in methanol conversion, while the selectivity to acetaldehyde decreases from 56% to 43% in ethanol conversion, when the reaction temperature is increased from 250 to 400 °C.