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Plasmonic nanostructures have played a key role in extending the activity of photocatalysts to the visible light spectrum, preventing the electron–hole combination and providing with hot electrons to the photocatalysts, a crucial step towards efficient broadband photocatalysis. One plasmonic photocatalyst, Au/TiO₂, is of a particular interest because it combines chemical stability, suitable electronic structure, and photoactivity for a wide range of catalytic reactions such as water splitting. In this review, we describe key mechanisms involving plasmonics to enhance photocatalytic properties leading to efficient water splitting such as production and transport of hot electrons through advanced analytical techniques used to probe the photoactivity of plasmonics in engineered Au/TiO₂ devices. This work also discusses the emerging strategies to better design plasmonic photocatalysts and understand the underlying mechanisms behind the enhanced photoactivity of plasmon-assisted catalysts.