In this work, titanium-doped mesoporous Al2O3 (-Ti-Al2O3) was prepared by an evaporation-induced self-assembly method and used as a carrier of Ba/-Ti-Al2O3 catalyst to catalyze the aldol condensation of methyl acetate with formaldehyde to methyl acrylate in a fixed-bed reactor. The catalysts were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, N-2 adsorption-desorption, pyridine absorption performed via Fourier transform infrared spectroscope (Py-IR), and NH3 and CO2 temperature-programmed desorption (NH3 and CO2-TPD). Experimental results indicated that the doping of the titanium species into the frame work of mesoporous Al2O3 (-Ti-Al2O3) had a significant influence on the catalytic activity via modifying the acid-base surface properties of the catalyst. Furthermore, the Ba/-Ti-Al2O3 catalyst demonstrated excellent catalytic performance, with a methyl acetate conversion rate of 50% and methyl acrylate selectivity up to 90.2%. Compared with the Ba/Al2O3 catalyst, the Ba/-Ti-Al2O3 catalyst had better catalytic activity, stability and potential for practical application, which was likely due to an increased number of Lewis acid sites, especially the medium acid sites.Graphical AbstractBarium supported mesoporous -Ti-Al2O3 catalyst was found to be an effective catalyst for vapor phase aldol condensation of methyl acetate with formaldehyde. [GRAPHICS] .