Rare earth (RE) ions (Eu3+,Tb3+) doped uniaxially aligned HfO2 nanotubes were prepared by radio frequency sputtering with electrospun polyvinylpyrolidone (PVP) nanofiber templates. The as-sputtered samples were annealed at different temperatures (500–1000 °C) in O2 ambient in order to remove their PVP cores and make the HfO2 shells well crystallized. Morphologies and crystal configuration of the samples were investigated by optical microscope, scanning electron microscopy, transmission electron microscopy, x–ray diffraction, and Raman spectroscopy. The nanotubes have uniform intact structure with an average diameter of 200 nm and a wall thickness of about 25 nm. Photoluminescence (PL) properties of the RE doped nanotubes have been studied in detail. The emission peaks of the aligned HfO2:Eu and HfO2:Tb nanotubes could correspond to the 5D0→7FJ (J=0–2) transitions of Eu3+ and the 5D4→7FJ (J=3–6) transitions of Tb3+, respectively. The PL intensities of the HfO2:RE3+ nanotubes were higher by several orders of magnitude than that of the films. This enhancement in the PL could be ascribed to the high density of surface states of HfO2:RE3+ nanotubes.