It is a subject of exploration whether the phase pure anatase or rutile TiO 2 or the band alignment due to the heterojunctions in the two polymorphs of TiO 2 plays the determining role in efficacy of a photocatalytic reaction. In this work, the phase pure anatase and rutile TiO 2 have been explored for photocatalytic nitroarenes reduction to understand the role of surface structures and band alignment towards the reduction mechanism. The conduction band of synthesized anatase TiO 2 has been found to be more populated with electrons of higher energy than that of synthesized rutile. This has given the anatase an edge towards photocatalytic reduction of nitroarenes over rutile TiO 2 . The other factors like adsorption of the reactants and the proton generation did not play any decisive role in catalytic efficacy.