In this paper, we demonstrate that angstrom thick single atomic layer deposited (ALD) ZnO passivation can signifcantly improve the photoelectrochemical (PEC) activity of hydrothermally grown TiO2 NWs. It is found that this ultrathin ZnO coating can passivate the TiO2 surface defect states without hampering the carrier’s transfer dynamics. Moreover, a substantial improvement can be acquired by changing the deposition temperature of the ZnO layer (80°C, and 250°C) and named as 80°C TiO2-ZnO, and 250°C TiO2-ZnO. It was found that the deposition of this single layer in lower temperatures can lead to higher PEC activity compared to that deposited in higher ones. As a result of our PEC characterizations, it is proved that photoconversion efciency of bare TiO2 NWs can be improved by a factor of 1.5 upon coating it with a single ZnO layer at 80°C. Moreover, considering the fact that this layer is a passivating coating rather than a continuous layer, it also keeps the PEC stability of the design while this feature cannot be obtained in a thick shell layer case. This paper proposes a bottom up approach to control the electron transfer dynamics in a heterojunction design and it can be applied to other metal oxide combinations.