In this work, a stratagem of improving the photocatalytic performance of TiO 2 under NIR irradiation was illustrated by the combination of TiO 2 with upconversion (UC) luminescent materials that present high intensity of UV band emission resulted from the sublattice energy clusters in tetragonal LiYF 4 : Tm UC matrix. The sublattice energy clusters were constructed by doping high concentration Yb 3 + into tetragonal LiYF 4 : Tm. 347 nm emission intensity of Tm 3 + were enhanced dramatically with the rising of Yb 3 + doping concentration and reached the top while 70% Yb 3 + was doped, and the intensity was enhanced about 6.15 times compared with that of the usual 20% Yb 3 + doped. After being coated with TiO 2 , 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.[a] Y.