A　catalyst　composed　of　monolayer　nonstoichiometric　titanate　nanosheets　(denoted　as　TN)　and　Pd　clusters　is　constructed　for　precise　synthesis　of　cyclohexanone　from　phenol　hydrogenation　with　high　conversion　(＞99%)　and　selectivity　(＞99%)　in　aqueous　media　under　light　irradiation.　Experimental　and　DFT　calculation　results　reveal　that　the　surface　exposed　acid　and　basic　sites　on　TN　could　interact　with　phenol　molecules　in　a　nonplanar　fashion　via　a　hexahydroxy　hydrogen-bonding　ring　to　form　a　surface　coordination　species.　This　greatly　facilitates　the　adsorption　and　activation　of　phenol　molecules　and　suppresses　the　further　hydrogenation　of　cyclohexanone.　Moreover,　the　surface　Pd　clusters　serve　as　the　active　sites　for　the　adsorption　and　dissociation　of　hydrogen　molecules　to　provide　active　H　atoms.　The　synergistic　effect　of　the　surface　coordination　species,　TN　and　Pd　clusters　remarkably　facilitate　the　high　yield　of　cyclohexanone　in　photocatalysis.　Finally,　the　possible　thermo/photocatalytic　mechanisms　on　Pd/TN　are　proposed.　This　work　not　only　highlights　the　great　potential　for　monolayer　nonstoichiometric　composition　nanosheets　in　the　construction　of　catalysts　for　precise　organic　synthesis　but　also　provides　insight　into　the　inherent　catalytic　behavior　at　a　molecular　level.　©　2017　American　Chemical　Society.