With increasing pollution of water resources and demand for hydrogen energy, photocatalysis, as a "green chemistry" technology, has attracted great attention. To meet the practical application requirements, photocatalysts should possess enhanced efficiency and be of low cost. Here, a novel Z-scheme ternary ZnTiO3/Zn2Ti3O8/ZnO heterojunction has been prepared by a solvothermal-calcination process. The phase transformation process of the sample can be defined as two processes, dehydration and thermal decomposition (ZnTiO3 → Zn2Ti3O8 + ZnO). The ZnTiO3/Zn2Ti3O8/ZnO heterojunction produced in this facile phase transformation strategy displayed highly efficient photocatalytic performance in water splitting for hydrogen production and pollutant removal, e.g. phenol, dye, and heavy metal Cr(vi). On the basis of the PL spectra, photocurrent response, radical trapping experiments and ESR tests, we found that a nontraditional transport of photoinduced carriers created by a single Z-scheme mechanism played a significant role in the efficient removing of target pollutants and hydrogen generation. This work provides a facile phase transformation approach to construct a Z-scheme semiconductor heterostructure system with high efficiency for hydrogen production and water pollution treatment.