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In this work, we demonstrate that vertically grown ZnO nanowire (NW) arrays of the wurzite phase were successfully fabricated on fluorine doped tin oxide (FTO) substrates via a hydrothermal method. The coating of a seed layer onto the FTO substrates was found to favor the growth of a uniform ZnO NWs array which shows saturation in the photocurrent density with a relatively low potential bias. Furthermore, prolonging the calcination time of the seed layer makes the ZnO NWs behave the better charge separation and improve the photo-electrochemical performance. Under the irradiation at a 75 mW cm −2 from a simulated sunlight source, the ZnO NWs array electrode prepared from the seed layer with calcination at 350 °C for 5 h shows a saturated photocurrent density of 514 μA cm −2 and a maximum half-cell solar-to-hydrogen (HC-STH) efficiency of 0.26% was obtained at 0.6 V versus reversible hydrogen electrode (RHE) in neutral electrolyte. [ABSTRACT FROM AUTHOR]