In this paper, evidence is provided that the model reaction of aqueous dihydroxyacetone (DHA) conversion is as sensitive to the TiO₂ catalysts’ basicity as to their acidity. Two parallel pathways transformed DHA: while the pathway catalyzed by Lewis acid sites gave pyruvaldehyde (PA) and lactic acid (LA), the base-catalyzed route afforded fructose. This is demonstrated on a series of six commercial TiO₂ samples and further confirmed by using two reference catalysts: niobic acid (NbOH), an acid catalyst, and a hydrotalcite (MgAlO), a basic catalyst. The original acid-base properties of the six commercial TiO₂ with variable structure and texture were investigated first by conventional methods in gas phase (FTIR or microcalorimetry of pyridine, NH₃ and CO₂ adsorption). A linear relationship between the initial rates of DHA condensation into hexoses and the total basic sites densities is highlighted accounting for the water tolerance of the TiO₂ basic sites whatever their strength. Rutile TiO₂ samples were the most basic ones. Besides, only the strongest TiO₂ Lewis acid sites were shown to be water tolerant and efficient for PA and LA formation.