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Currently, hydrogen generation via photocatalytic water splitting using semiconductors is regarded as a simple environmental solution to energy challenges. This paper discusses the effects of the doping of noble metals, Ir (3.0 at.%) and Ni (1.5–4.5 at.%), on the structure, morphology, optical properties, and photoelectrochemical performance of sol-gel-produced SnO₂ thin films. The incorporation of Ir and Ni influences the position of the peaks and the lattice characteristics of the tetragonal polycrystalline SnO₂ films. The films have a homogeneous, compact, and crack-free nanoparticulate morphology. As the doping level is increased, the grain size shrinks, and the films have a high proclivity for forming Sn–OH bonds. The optical bandgap of the un-doped film is 3.5 eV, which fluctuates depending on the doping elements and their ratios to 2.7 eV for the 3.0% Ni-doped SnO₂:Ir Photoelectrochemical (PEC) electrode. This electrode produces the highest photocurrent density (<i>J_ph</i> = 46.38 mA/cm²) and PEC hydrogen production rate (52.22 mmol h⁻¹cm⁻² at −1V), with an Incident-Photon-to-Current Efficiency (IPCE% )of 17.43% at 307 nm. The applied bias photon-to-current efficiency (ABPE) of this electrode is 1.038% at −0.839 V, with an offset of 0.391% at 0 V and 307 nm. These are the highest reported values for SnO₂-based PEC catalysts. The electrolyte type influences the <i>J_ph</i> values of photoelectrodes in the order <i>J_ph</i>(HCl) > <i>J_ph</i>(NaOH) > <i>J_ph</i>(Na₂SO₄). After 12 runs of reusability at −1 V, the optimized photoelectrode shows high stability and retains about 94.95% of its initial PEC performance, with a corrosion rate of 5.46 nm/year. This research provides a novel doping technique for the development of a highly active SnO₂-based photoelectrocatalyst for solar light-driven hydrogen fuel generation.