The　selective　reduction　of　nitroaromatics　has　long　been　the　focus　of　fundamental　and　practical　interest.　The　challenging　issue　lies　in　how　to　finely　control　the　product　selectivity.　Herein,　we　report　a　light-assisted　thermocatalytical　process　to　convert　nitrobenzene　into　azobenzene　and　hydrazobenzene　with　high　selectivity　and　high　yields　by　simply　controlling　the　reaction　time.　The　light-enhanced　efficiency　of　Au/TiO2　catalyst　is　up　to　14.8%　at　90　°C　due　to　the　localized　surface　plasmon　resonance　(LSPR)　effect　of　Au　nanoparticles.　Moreover,　the　hydrogen-delivery　rate　here　is　much　faster　than　that　of　current　reported　systems.　The　reaction　mechanism　was　also　investigated　by　EPR　technique,　where　Au–H　intermediate　species　is　found　to　account　for　the　high　efficiency　in　this　reduction　process.　The　favorable　results　demonstrated　that　plasmon-enhanced　catalytic　reaction　might　be　more　attractive　and　applicable　in　industrial　organic　synthesis.　©　2019　Elsevier　B.V.