CaF2:Ln(3+) (Ln = Ce, Tb, Eu) phosphors with highly uniform shapes have been successfully synthesized by a simple hydrothermal method directly. The as-prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL) and lifetime. The results indicated that the pH values, organic additive and reaction time have a significant effect on the morphology and dimensions of CaF2 microcrystals and the possible formation mechanism was also proposed. Furthermore, the energy transfer from Ce3+ to Tb3+ and from Tb3+ to Eu3+ and from Ce3+ to Tb3+ to Eu3+ was observed and the corresponding mechanisms were discussed in detail. The CaF2:Ln(3+) phosphors may have potential optical applications in near-UV and violet LEDs.