Vanadium sulphide is an emerging infrared active photocatalyst that has not been utilized to its maximum potential. Herein, we report the application of highly textured photon trapping infrared active vanadium sulphide nanowalls sensitized with visible active CdS nanoparticles supported on ultraviolet (UV) active TiO₂ nanorods to obtain a wide range of light absorbance throughout the solar spectrum for maximum solar energy utilization. The vanadium sulphide nanowall/TiO₂ nanorod heterostructures were fabricated by a two-step hydrothermal approach followed by CdS sensitization by a successive ionic layer adsorption reaction (SILAR) process. Photoelectrochemical performance was analyzed using simulated solar irradiation (AM 1.5G, 100 mW cm⁻²) with potential linear sweep voltammetry. A maximum Applied Bias to Photocurrent Efficiency (ABPE) of 1.34% was observed at 0.58 V. It was interestingly noted that the photoanode performance decreased with an increase in CdS loading over 20 deposition cycles. The IPCE response of this photoanode confirmed high photoelectrochemical responses throughout the solar spectrum. Electrochemical impedance spectroscopy (EIS) and Mott–Schottky (MS) plots were used to analyze the charge transport process and electrode kinetics of the fabricated photoanodes. Stability analysis was carried out using chronoamperometry. DFT calculations and ray-tracing simulations were carried out to study the nanotexture effect on light absorption, band alignment, charge transfer pathways, and overall intricate electronic properties of the heterostructure. The nanostructure and crystal morphology were analyzed using different characterization tools. Our result represents the importance of fabrication of semiconductor heterostructures with high light absorption capabilities and efficient charge transport resulting from optimum band alignment, heterostructure designing and preferentially tailored nanotextured morphology.