Based on a facile vapor-phase transport method without any catalyst and template, one-dimensional single-crystalline bismuth oxide (Bi2O3) micro/nanoribbons were fabricated on silicon substrates in large quantities and morphology-controlled fabrication of Bi2O3 was achieved from a single precursor. The widths of Bi2O3 ribbons varied from 0.2 to 20 microm depending on the deposition temperatures. The thickness was in the range of 0.1-2 microm and the length reached several hundred micrometers and even millimeter range. The detailed composition and structural analysis confirmed the single-crystalline nature of alpha-Bi2O3 micro/nanoribbons with monoclinic structure. The photoluminescence spectrum of a single Bi2O3 ribbon showed a broadband emission from 450 to 750 nm in the visible region, consisting two peaks located at 589 and 697 nm which were primarily originated from the impurity ions and crystal defects. A self-catalyzed vapor-solid model was proposed to account for the growth mechanism of Bi2O3 ribbons with different morphologies.