In this study, we have synthesized nanostructured titanium dioxide (TiO2) photocatalysts under different configurations, viz., anatase, rutile and anatase/rutile heterophase (Eg = 3.14-2.96 eV) through a sol-gel route. The photocatalytic performance of the heterophase samples was better than that of their phase-pure counterparts. Photocatalytic performance was maximum for sample T12H (50% rutile) with a rate constant, k = (7.38 ± 1.48) × 10-2 min-1. This is ca. 47% greater than that estimated via an extrapolation method using the values for phase pure samples indicating synergistic effects. High-resolution transmission electron microscope (HRTEM) analysis and the phase-dependent broadening of core-level X-ray photoelectron spectroscopy (XPS) analysis indicate the formation of well-defined anatase/rutile interfaces. Interfacial charge transfer is the critical factor for this synergistic effect. To analyze the charge transfer pathways, the possible band alignment scheme was analyzed through the precise determination of band alignments from XPS, employing the Ti 2p3/2 core level as a reference. We found a staggered rutile band alignment with the valence band edge of rutile lying above that of anatase, indicating the transfer of photogenerated free electrons from the conduction band of rutile to that of anatase and hole transfer from the valence band of anatase to rutile. These inferences are validated through Mott-Schottky analysis as well.