Yttrium tungstate precursors with novel 3D hierarchical architectures assembled from nanosheet building blocks were successfully synthesized by a hydrothermal method with the assistance of sodium dodecyl benzenesulfonate (SDBS). After calcination, the precursors were easily converted to Y₂(WO₄)₃ without an obvious change in morphology. The as-prepared precursors and Y₂(WO₄)₃ were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM), and photoluminescence (PL) spectra, respectively. The results reveal that the morphology and dimensions of the as-prepared precursors can be effectively tuned by altering the amounts of organic SDBS and the reaction time, and the possible formation mechanism was also proposed. Upon ultraviolet (UV) excitation, the emission of Y₂(WO₄)₃:x mol% Eu³⁺ microcrystals can be tuned from white to red, and the doping concentration of Eu³⁺ has been optimized. Furthermore, the up-conversion (UC) luminescence properties as well as the emission mechanisms of Y₂(WO₄)₃:Yb³⁺/Ln³⁺ (Ln = Er, Tm, Ho) microcrystals were systematically investigated, which show green (Er³⁺, ⁴S_3/2, ²H_11/2 → ⁴I_15/2), blue (Tm³⁺, ¹G₄ → ³H₆) and yellow (Ho³⁺, ⁵S₂ → ⁵I₈) luminescence under 980 nm NIR excitation. Moreover, the doping concentration of the Yb³⁺ has been optimized under a fixed concentration of Er³⁺ for the UC emission of Y₂(WO₄)₃:Yb³⁺/Er³⁺.