Nanoerythrocyte-like, dodecahedron and nanoparticle HoVO 4 with high uniform size had been successfully synthesized on a large scale by a simple and facile complex agent assisted hydrothermal method. The nanoerythrocyte-like HoVO 4 was characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, field-emission scanning electron microscopy, high-resolution transmission electron microscopy, and photoluminescence. The possible formation mechanism of the nanoerythrocyte-like HoVO 4 was proposed. The PL results showed the pure HoVO 4 products with different size and morphology displayed the same emission band with diverse relative intensity under the excitation of 455nm and the red emission transition 5 F 5 → 5 I 8 was the most prominent group, whose peak situated at 659nm. Furthermore, this general and facile method may be applied in the synthesis of other lanthanide compounds with nanoerythrocyte-like morphology.