A　multifunctional　photocatalyst　is　constructed　based　on　Cu-Cu2O　hybrid　and　monolayer　H1.4Ti1.65O4·H2O　nanosheets　via　an　in　situ　photo-deposition　process　(Cu-Cu2O/TNS).　The　prepared　sample　enables　the　oxidation　of　cinnamyl　alcohol　to　cinnamaldehyde　with　over　95%　of　selectivity　under　visible　light　irradiation　using　molecule　O2　as　the　oxidant.　In　situ　FTIR　spectra　suggest　that　the　Lewis　acid　sites　in　TNS　would　selectively　adsorbed　the　hydroxyl　of　cinnamyl　alcohol　forming　surface　–C–OTi–O–　coordination　species.　UV-DRS　spectra　reveal　that　light　adsorption　of　TNS　can　be　extended　to　visible　light　region　due　to　the　interface　charges　transfer　from　–C–OH　to　Ti–O–　via　the　surface　coordination,　resulting　in　the　activation　of　–OH　in　alcohol.　In　situ　ESR　further　indicates　that　directional　interface　charge　transfer　induces　the　charge　enrichment　in　Ti　atoms　of　TiO6,　facilitating　O2　adsorption.　XAFS　results　reveal　that　the　hybrid　electronic　states　of　Cu-Cu2O　efficiently　improve　the　interface　electronic　transfer　kinetics　to　inhibit　the　intramolecular　hydrogen　transfer　for　dominating　the　selectivity　towards　cinnamaldehyde.　This　work　highlights　the　synergistic　effect　of　surface　coordination-activation-photocatalysis　for　selective　photosynthesis　of　fine　chemicals.　©　2019　Elsevier　Inc.