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In this study, we have synthesized hierarchical TiO2@In2O3 heteroarchitecture photoanodes via a hydrothermal method and studied their interfacial charge carrier dynamics through water splitting and organic decomposition. Photoelectrochemical measurements show that the IN-0.4 exhibits an obvious enhancement in photocurrent density compared to the pristine TiO2. Electrochemical impendence spectroscopy (EIS) and Time-resolved photoluminescence (PL) have been employed to study the charge recombination in TiO2@In2O3 nanostructure. The surface passivation of TiO2 nanorods (NRs) with In2O3 nanostructures helps to the suppression of the surface defects. The surface-passivated photoanode (IN-0.4) has demonstrated the improved hydrogen generation activity (125 μmol∙h−1) of TiO2 nanorods (NRs) with In2O3 nanostructures during water splitting and organic decomposition. The probable causes of the enhancement in hydrogen evolution could be due to (i) enhanced photogenerated electron transport (ii) increased active surface area with In2O3 and/or (iii) catalytic activity of In2O3. Moreover, the photoelectrocatalytic activities of IN-0.4 were slight affect during degradation of Bisphenol A and methyl orange dye, which might be due to the lower hole mobility in TiO2@In2O3 heteroarchitecture photoelectrodes. These sightings and proposed schematic model can help to understand the charge transfer dynamics in hierarchical TiO2@In2O3 heteroarchitecture photoelectrodes as well as designing multifaceted photoelectrodes for solar energy conversion.