A bimetallic CuPd/TiO2 system has been prepared by a two‐step synthesis and was used for a methanol steam photoreforming reaction. By sequential deposition, palladium is deposited over copper nanoclusters through a galvanic replacement process. Hydrogen production by steam reforming from methanol was achieved by both thermo‐photocatalytic and photocatalytic processes. It appears that H2 production on the bimetallic system is notably higher than the Pd monometallic reference. Moreover this difference in the catalytic performance could be related to the higher CO evolution observed for the monometallic Pd1.0 TiO2 system which is partially inhibited in the bimetallic catalyst. In addition, an important thermal effect can be envisaged in all cases. Nevertheless, this improved effect in the thermo‐photocatalytic process is accompanied by a remarkable CO evolution and SMSI effect (important strong metal‐support interactions) that hindered the efficiency as temperature increases. On this basis, optimal operational conditions for H2 production are obtained for thermo‐photocatalytic reforming at 100 °C, for which the synergetic effect is higher with lower CO production (H2/CO=4).