The effects of the parameters of the sol–gel catalyst preparation such as hydrolysis ratio, acid/alkoxide ratio, and calcination temperature on surface area, porous structure, crystal structure and surface properties of nickel–titanium (Ni–Ti) composite xerogel catalyst were studied. The optimum hydrolysis ratio and acid/alkoxide ratio were determined under which conditions and 453K calcination temperature, a Ni–Ti xerogel catalyst with a surface area of 426m2/g was made. Increasing the calcination temperature would lead to dramatic decrease in surface area and collapse in porous structures. To compensate this deleterious effect, aluminum-containing compound was added into the precursor mixture in sol–gel preparation and the resultant Ni–Ti–Al composite xerogel catalyst had a significantly higher surface area even after undergoing a calcination temperature as high as 973K. This xerogel catalyst showed comparably high activity for carbon dioxide reforming of methane where high temperature calcination is inevitable.