With the advent of nanotechnology there has been a resurge of interest in alpha-Fe2O3, as suitable candidate for photoelectrochemical (PEC) splitting of water to generate hydrogen. This paper describes the enhanced PEC behaviour of nanostructured alpha-Fe2O3 thin films modified by various techniques. Nanostructured thin film/pellets of alpha-Fe2O3 Prepared by various techniques and various dopants were investigated for their photoelectrochemical response. Thin films prepared by spray pyrolysis having particle size of 20-30 nm exhibited better photoresponse as compared to the films prepared by sol-gel methods, which further improved on doping with Zn. These films were further modified by (i) depositing Zn dots on the surface of alpha-Fe2O3 films using thermal evaporation method and (ii) irradiating it with 170 MeV Au13+ ions. When used as electrode in photoelectrochemical cell, a significant increase in the photoresponse of these modified films were observed, details of which are discussed. (C) 2007 International Association for Hydrogen Energy.