Commercial and home prepared TiO₂ samples were functionalized with a commercial Keggin heteropolyacid (HPA) H₃PW₁₂O₄₀ (PW₁₂) or with a hydrothermally home prepared K₇PW₁₁O₃₉ salt (PW₁₁). All the materials were characterized by specific surface area measurements (BET), XRD analyses, Raman, DRS along with SEM observations and they have been used for glucose photocatalytic conversion in an aqueous suspension. Different reaction extents and distribution of intermediate oxidation products were observed depending on the photocatalyst. Gluconic acid, arabinose, erythrose and formic acid were observed as oxidation products when bare TiO₂ or HPA/TiO₂ composite materials were used. Glucose isomerization to form fructose was also observed and in some runs traces of glucaric acid and glyceraldehyde were also found. The carbon mass balance was accomplished in the presence of the commercial Evonik P25 TiO₂ powder and the composites where TiO₂ was present, whereas the presence of the solvothermically prepared TiO₂ gave rise to a carbon unbalance, due to strong adsorption of the products on the photocatalyst surface. No reactivity was observed in the presence of PW₁₂ alone while PW₁₁ induced only isomerization of the glucose.