Nanostructured hematite thin films were doped with zirconium successfully using electrodeposition method for their implementation as photoanode in photoelectrochemical (PEC) cell for hydrogen generation. XRD, Raman, XPS, SEM and UV-visible spectroscopy techniques were used to characterize the thin films. Highest photocurrent density of 2.1 mA/cm(2) at 0.6 V/SCE was observed for 2.0 at.% Zr4+ doped alpha-Fe2O3 sample with solar to hydrogen conversion efficiency of 1.43%. Flatband potential (-0.74 V/SCE) and donor density (2.6 x 10(21) cm(-3)) were found to be maximum for the same sample. These results suggest substantial potential of hematite thin films with controlled doping of zirconium in PEC water splitting applications. (C) 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.