In　this　work,　a　stratagem　of　improving　the　photocatalytic　performance　of　TiO2　under　NIR　irradiation　was　illustrated　by　the　combination　of　TiO2　with　upconversion　(UC)　luminescent　materials　that　present　high　intensity　of　UV　band　emission　resulted　from　the　sublattice　energy　clusters　in　tetragonal　LiYF4:　Tm　UC　matrix.　The　sublattice　energy　clusters　were　constructed　by　doping　high　concentration　Yb3+　into　tetragonal　LiYF4:　Tm.　347nm　emission　intensity　of　Tm3+　were　enhanced　dramatically　with　the　rising　of　Yb3+　doping　concentration　and　reached　the　top　while　70%　Yb3+　was　doped,　and　the　intensity　was　enhanced　about　6.15　times　compared　with　that　of　the　usual　20%　Yb3+　doped.　After　being　coated　with　TiO2,　the　photocatalytic　performance　of　the　complex　was　enhanced　about　2.55　folds　compared　to　P25.　XRD,　SEM,　TEM,　FTIR,　UV-vis　and　fluorescence　spectrum　were　employed　for　the　systematical　investigation　of　the　relationship　between　structure　and　performance.　This　stratagem　may　be　helpful　for　the　design　and　preparation　of　photocatalysts　and　photo　sensors.