In this study, a novel photocatalyst, Ptx-/TiO2-yBy, is prepared by-impregnation of a B4O72- anion solution coupled with a new type of water splitting system for hydrogen evolution. The results show that the B4O72- anion solution is a very good system for B-doping Pt/TiO2 photocatalyst preparation. The particular advantages of this preparation method are that the incorporation of B into Pt/TiO2 can be achieved via coupling with the photocatalytic reaction and that the doping of B into photocatalyst Pt/TiO2 results in the negative shift of Pt binding energy and the efficient reduction of H+ to H-2, even though no sacrificial electron donor existed. In the study of photocatalysis, it is found that the B4O72- anion solution is a newly efficient water splitting environment. The rate of hydrogen evolution increases with addition of B4O72- anion. On the basis of the studies of photoelectrochemical properties in this system, the interesting phenomenon is found that interval illumination may enhance the rate of hydrogen evolution. Moreover, the B-doped TiO2 exhibits somewhat of a red-shift.