In this work, we reported the fabrication and characterization of CaWO4:Ln3+/Na+ (Ln = Nd, Er, and Yb) core/shell microspheres via a facile hydrothermal method in the presence of citric acid and PVP. The samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, infrared spectra, and photoluminescence. It's found that citric acid could modulate the nucleation and growth of CaWO4 nanocrystals and enable the co-incorporation of Na+ and Ln3+ (Ln = Nd, Er, and Yb) into CaWO4 lattice. Meanwhile, PVP controlled the assembly of CaWO4 nanocrystals into a core/shell spherical structure. All CaWO4:Ln3+/Na+ (Ln = Nd, Er, and Yb) core/shell microspheres exhibited intense near-IR luminescence. In comparison with CaWO4:Ln3+/Na+ nanocrystals, the self-assembled core/shell nanoarchitechtures showed highly enhanced IR luminescent properties due to the depressing of surface energy-loss.