We report on the synthesis and characterization of folic acid-conjugated silica-modified TbPO4·H2O nanorods for biomedical applications. The uniform shape TbPO4·H2O nanorods with a hexagonal phase were successfully synthesized by wet chemical methods. A novel TbPO4·H2O@silica-NH2 nanocomplex was then formed by functionalizing these nanorods with silica and conjugating with biological agents. The field emission scanning electron microscopy, energy-dispersive X-ray, and X-ray diffraction reveal the morphology and structure of the nanorods, with their controllable sizes (500-800 nm in length and 50-80 nm in diameter). The Fourier transform infrared spectroscopy was employed to identify chemical substances or functional groups of the TbPO4·H2O@silica-NH2 nanocomplex. The photoluminescence spectra show the four emission lines of TbPO4·H2O@silica-NH2 in folic acid at 488, 540, 585, and 621 nm under 355 nm laser excitation, which could be attributed to the 5D4-7
F
j
(
J
=
6
,
5
,
4
,
3
) transitions of Tb3+. The TbPO4·H2O@silica-NH2 nanorods were conjugated with folic acid for the detection of MCF7 breast cancer cells. The obtained results show a promising possibility for the recognition of living cells that is of crucial importance in biolabeling.