One-dimensional (1D) Gd2O3:Eu3+ nano-rods and micro-rods were prepared using a facile sol-gel precipitation method, without a template and with a post-growth heat treatment in air. Based on scanning electron microscopy (SEM) and X-ray diffraction (XRD) data, hexagonal Gd(OH)3:Eu3+ micro-rods, 60∼90 nm in diameter and 700 nm to 1 μm in length, were synthesized and then transformed by calcining (800°C, 2 hr) to cubic Gd2O3:Eu3+ with the same morphology and dimensions. Nano-rods of Eu3+ doped Gd(OH)3 and calcined Gd2O3, 60∼90 nm diameter and 150∼300 nm length, were prepared by adding polyethylene glycol (PEG) as a capping agent during the sol-gel synthesis. Photoluminescence (PL) spectra exhibited the 5D0–7F2 transitions of Eu3+ at 612 and 627 nm from excitation at 280 nm. Photoluminescence excitation (PLE) data showed that a small fraction of PL from Eu3+ resulted from direct excitation, but most PL resulted from the oxygen to europium charge-transfer band (CTB) between 250 and 280 nm.