Near-infrared-to-ultraviolet (NIR-to-UV) multiphoton upconversion has recently received increasing attention owing to its promising frontier applications in the fields of biomedicine and nanophotonics. However, the realization of high-efficiency NIR-to-UV upconversion remains a dispiriting challenge due to weak excitation light harvesting and photo-conversion efficiency. Herein, we propose a mechanistic strategy to achieve intensified UV upconversion by manipulating the injected excitation energy flux. A simple LiYbF4:Tm@LiYF4 host-sensitized sublattice core-shell nanostructure was initially proposed to compete with the concentration quenching effect and increase energy transfer efficiency. Then, the organic dye ICG was further coated to introduce the antenna sensitization effect to highly increase the absorption ability of nanocrystals. After optimizing the ICG number loaded on the surface and separation distance, up to 167-fold UV upconversion emission enhancement was achieved under low-power excitation of 808 nm. More importantly, the efficient UV upconversion exhibits enhanced reactive oxygen species (ROS) generation activity by fabricating a TiO2-modified upconversion nanocomposite, revealing great application potential in frontier fields such as in vivo photodynamic therapy and bioimaging-guided therapeutics. Our results can provide versatile designs to achieve efficient UV upconversion, overcome conventional limitations, and offer exciting opportunities for potential applications in biomedical fields.