Photocatalytic application of the thermal catalyst Fe(2)O(3) in hydrogen production from H(2)S requires a chemical modification to lessen/avoid the chemical attack by H(2)S. Incorporating this objective, in the present work FeGaO(3) with equimolar Fe and Ga contents was prepared by solid state (SS) and hydrothermal (HT) routes. The resulting materials, FeGaO(3)-SS and FeGaO(3)-HT are found to have characteristically different crystalline structures and morphology. Their photocatalytic activities in the unloaded/pristine and 1 wt% NiO(x)-loaded forms as well as in the fresh and used conditions in hydrogen production from H(2)S under visible light (lambda >= 420 nm) reveal that the synthesized photocatalysts are stable in their functionalities and the trends are quite interesting and unusual. The structure-activity investigation clearly suggests the key role of their material configurations in deciding photofunctionalities. The fair quantum yields (7-9% at 550 nm), the regenerative and reusable features plus the scope for improvement through optimum Ga content, all make the new photocatalysts promising. (C) 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.