A variety of microstructured YF₃:Eu³⁺ with different morphologies have been successfully synthesized using a simple inorganic salt as the only structure-directing agent in the hydrothermal system. The cations of Al³⁺, Li⁺, Mg²⁺, Na⁺, K⁺ and Ba²⁺ were found to determine the size and morphology of the as-prepared microstructured YF₃. The prepared samples were systematically characterized by powder X-ray diffraction (XRD), field emission-scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), photoluminescence (PL) and photoluminescent excitation spectra (PLE). Detailed proofs indicated that the process of growing different morphologies of YF₃:Eu³⁺ microparticles were dominated by different growth mechanisms. Furthermore, photoluminescent properties were also investigated.