The　photoalkylation　of　nitroarenes　with　benzyl　alcohols　in　one　pot　at　room　temperature　and　1　atm　N　2　was　achieved　over　the　Pd/H　1.07　Ti　1.73　O　4　·H　2　O　nanosheets.　The　sample　shows　efficient　photocatalytic　activity　with　high　conversion　of　nitrobenzene　(99%)　and　selectivity　of　secondary　amine　(85%).　This　flexible　photocatalytic　system　is　also　applicable　to　other　nitroarenes　with　high　efficiency.　Results　of　in　situ　FTIR,　DRS,　and　in　situ　ESR　revealed　that　the　benzyl　alcohol　and　nitrobenzene　molecules　can　bind　with　the　surface　Lewis　and　Brønsted　acid　sites　in　the　catalyst　via　the　H–O⋯Ti　and　NO　2　⋯H–O–Ti　species.　The　formation　of　surface　coordination　species　results　in　not　only　the　activation　of　reactant　molecules　via　surface　electron　transfer,　but　also　the　expanded　visible　light　absorption　of　the　catalyst.　Moreover,　in　situ　ESR　suggested　that　the　surface　coordination　can　also　facilitate　the　formation　of　oxygen　vacancies　in　catalysts,　which　can　greatly　promote　the　exposure　of　Lewis　sites　and　enhance　the　activation　of　reactant　molecules.　Finally,　a　possible　hydrogen　transfer　strategy　over　the　sample　is　proposed　on　a　molecular　level.　©　2018　Elsevier　Inc.