Novel rare earth based 4,4′,4′′-benzene-1,3,5-triyl-tri-benzonate (RE-BTB) infinite coordination polymer (ICP) hollow microspheres have been successfully prepared viaa facile surfactant-free mixed-solvothermal route, among which Tb-BTB was studied in detail. These as-prepared hollow microspheres using terbium as the central ion have diameters of 260–500 nm. Influential factors such as reaction temperature, reaction time, dosage of reagents, and solvent composition on the morphology and size of the Tb-BTB ICP hollow spheres have been systematically investigated. An inside-out formation mechanism was proposed for the hollow microspheres. The photoluminescence properties of the Tb-BTB hollow spheres have been systematically studied. It turns out that it is easy to tune the luminescent characteristics of the Tb-BTB ICP hollow spheres within a wide spectral range by simply varying the excitation lines or the doping concentration of Eu3+. Interestingly, white-light emission was realized in the Eu3+doped Tb-BTB hollow spheres. [ABSTRACT FROM AUTHOR]