Gold (Au) nanoparticles were prepared by the electrochemical deposition of aqueous solution of auric chloride (AuCl₄) on the titanium dioxide (TiO₂) film. Before and after the electrochemical deposition, the TiO₂ film was soaked into dye solution of Rose Bengal. It is found that the photoelectrochemical properties were enhanced after the incorporation of Au nanoparticles along the TiO₂ film. Generally, the “hot electrons” were the main feature behind such properties and the hot electrons were the results of the incorporation of Au nanoparticles on the TiO₂ film that triggered the exothermic chemical process. Here dye molecules acted as a light absorber, where they converted the incoming photons from the sun rays into electron-hole pairs. The electron-hole pairs within TiO₂ showed the localized surface plasmon resonance (LSPR). In this process, the collective oscillations of free electrons confined at the metal surface (conductive substrates) were induced when the incoming incident frequency matched with collective oscillations of these free electrons and transferred them to the conduction band of semiconductor. This caused the enhancement of power conversion, i.e., photovoltage and photocurrent.