A hard template strategy is developed to fabricate the LuBO₃: Eu³⁺/Tb³⁺ hollow microspheres using a novel multi-step transformation synthetic route for the first time with polystyrene (PS) spheres as the template, followed by the combination of a facile homogeneous precipitation method, an ion-exchange process, and a calcination process. The results show that the as-obtained LuBO₃: Eu³⁺/Tb³⁺ hollow spheres have a uniform morphology with an average diameter of 1.8 μm and shell thickness of about 80 nm. When used as luminescent materials, the emission colors of LuBO₃: Eu³⁺/Tb³⁺ samples can be tuned from red, through orange, yellow and green–yellow, to green by simply adjusting the relative doping concentrations of the activator ions under the excitation of ultraviolet (UV) light, which might have potential applications in the field such as light display systems and optoelectronic devices.