Structure-based rational design of photocatalysts to enable combination of nanocomponents of radically different properties for enhanced solar energy utilization is a very challenging task. Herein, we integrated up-conversion material NaYF₄:Yb³⁺, Er³⁺, Tm³⁺ with TiO₂ shells and Ag nanoparticles to synthesise a new class of materials with good stability, broadband absorption from ultraviolet to near infrared, and excellent photocatalytic activity. Structure analysis proved that intimate contact between the NaYF₄:Yb³⁺, Er³⁺, Tm³⁺ core and the TiO₂ shell and between the TiO₂ shell and Ag NPs is the reason for the enhanced photocatalytic activity. Furthermore, the materials also showed exceptionally high stability and reusability under similar experimental conditions. All these results reveal that hierarchical core–shell microspheres exhibit great prospects for developing efficient solar photocatalysts.