Spin-polarized density functional theory calculations have been performed to understand the interactions in polyaniline (PAni) and TiO2 composite at the atomic level. Binding energy calculation shows that composite structure is energetically more stable when Ti atom of TiO2 sits on top of PAni. It is also found that there is a dependency of the CBM on the site of TiO2 interaction in this composite system. The results suggest that optimization of the synthesis parameters at atomic level can be an effective way to improve the performance of a photovoltaic device based on PAni-TiO2 composite. (C) 2015 Elsevier B.V. All rights reserved.