A highly three-dimensional CdIn2S4 deposited TiO2 (CdIS/TONR/FTO) heterostructured photoanode has been fabricated via a two-step hydrothermal process to enhance the photoelectrochemical (PEC) performance. In this work, bare TiO2 nanorods are grown successfully on the fluorine-doped fin oxide (FTO) substrate via a hydrothermal method (TONR/FTO), and a second-step hydrothermal synthesis is used to grow CdIn2S4 flower nanostructured layer over the top surface of the bare TONR/FTO. Structural, morphological, optical, and elemental analysis of CdIS/TONR/FTO heterostructure photoanode is investigated in detail. PEC performances are studied in 0.2 V versus Ag/AgCl in mixed sulfide-based electrolyte for various concentrations of CdIn2S4 deposited on photoanodes. The photocurrent density for optimized (x 4)-CdIS/TONR/FTO heterostructure photoanode is observed to be three times higher than that of the bare TONR/FTO photoanode. This excellent PEC performance is ascribed to the way that the deposited CdIn2S4 layer and TiO2 nanorods synergistically allow the absorption of a wide portion of the solar spectrum under back illumination, and provide efficient separation of the electronhole pairs in the photoanode architecture. The EIS and IMPS analysis also reveal the significance of CdIn2S4 layer that provides the lowest charge-transfer resistance at the interface and high electron-transfer rate in CdIS/TONR/FTO photoanode. Mainly, the deposited CdIn2S4 layer significantly broadens the optical absorption capacity, and provides efficient electrons-holes transfer that reduces the recombination losses of the charge carriers. The proposed charge transfer mechanism in CdIS/TONR/FTO heterojunction is well studied.