Tb(3+)-doped Gd(2)O(3) (Gd(2)O(3):Tb(3+)) nanofibers were prepared via a simple electrospinning technique using poly(ethylene oxide) (PEO) and rare-earth acetate tetrahydrates (Ln(CH(3)COO)(3)·4H(2)O (Ln = Gd, Tb)) as precursors. The obtained nanofibers have an average diameter of about 80 nm and are composed of pure cubic Gd(2)O(3) phase. A possible formation mechanism for the nanofibers is proposed on the basis of the experimental results, which reveals that PEO acts as the structure directing template during the whole electrospinning and subsequent calcination process. The luminescent properties of the nanofibers were investigated in detail. The nanofibers exhibit a favorable fluorescent property symbolized by the characteristic green emission (545 nm) resulting from the 5D4-->7F5 transition of Tb(3+). Concentration quenching occurs when the Tb(3+) concentration is 3 at.%, indicating that the Gd(2)O(3):Tb(3+) nanofibers have an optimum luminescent intensity under such a doping concentration.