In this work, BCN-TiO2(A + R) heterojunctions were constructed via a simple one-step calcination method as efficient photocatalysts for H-2 evolution. Simultaneously, an anatase/rutile phase-junction was also obtained due to the crystalline phase transformation that occurred during high-temperature calcination. The unique hetero-junction and phase-junction lead to the formation of an intimate interface and large contact area between two semiconductors and extended the visible-light absorption range. Therefore, BCN-TiO2(A + R) heterojunctions with a mixed anatase and rutile phase exhibit enhanced photocarrier separation efficiency, realizing an elevenfold increase in the electron lifetime compared to that of pure TiO2 and yielding a remarkable visible-light-driven H-2 evolution rate nearly 7.5 and 12.2 times higher than that of TiO2(A + R) and pure BCN, respectively. This work provides a new strategy for designing efficient water-splitting photocatalysts with highly efficient charge separation and transfer.