Polyhedral YVO4: Ln3+ (Ln = Eu, Sm, Yb/Er, Yb/Tm) microcrystals were fabricated via a facile sol–gel auto-combustion method using NH4VO3 as vanadium source in the presence of glycine. The X-ray diffraction patterns were well matched with pure YVO4, and the doped lanthanide ions did not change the host structure. The YVO4 microcrystals annealed from 500 to 1000 °C for 3 h were polyhedral and ranged in particle size from 0.1 to 2 μm. The luminescence properties of YVO4: Ln3+ (Ln = Eu, Sm, Yb/Er, Yb/Tm) samples indicated that all of the YVO4: Ln3+ samples exhibited typical emission spectra of Ln3+ cations, suggesting that the Ln3+ cations were well doped in YVO4 and could be excited efficiently through matrix absorption. In addition, the corresponding mechanisms of emission and energy transfer in the YVO4: Ln3+ are proposed.