The conversion of ethanol towards ethylene and diethyl ether in the presence of catalysts requires special consideration from the perspective of green chemistry. Ethanol dehydration was studied on a complex titanium phosphate MAlTiP (M_0.5(1+x)Al_xTi_2-x(PO₄)₃ with M = Ni, Mn (x = 0; 0.2)) catalysts, alongside a NASICON-type structure synthesized by the sol–gel method. The initial catalysts were characterized by N₂ gas sorption, SEM, XRD and spectroscopic methods (Raman and DRIFT of adsorbed CO and C₆H₆). The results revealed that all catalysts exhibited high activity and selectivity at 300–420 °C. The conversion of ethanol increases with the reaction temperature, reaching 67–80% at 420 °C. The MnAlTiP exhibited the highest ethylene selectivity among other catalysts, with 87% at 420 °C. The aluminum modification improved the acid properties of the catalysts, due to the appearance of Lewis acid sites (LAS) and the strength moderate Brønsted acid sites (BAS). It was shown that the activity of complex phosphates in ethanol dehydration increases with the strength of the Brønsted acid sites (BAS).