Long alpha-TeO2 microwires were synthesized in high yield on quartz substrate by vapor transport process, using Te powder as the source material and oxygen (O-2) as a carrier gas. Scanning electron microscope (SEM). X-Ray diffraction (XRD). transmission electron microscopy (TEM) and selected area diffraction patterns (SAD) were employed to characterize the microstructures obtained at different growth time steps in order to propose a possible growth mechanism of microwires. Irregular microparticles were first formed on the quartz substrate surface and then they acted as self-catalytic center for the growth of smooth microwires with diameters in the range 2-4 mu m and lengths up to 300 mu m. As heating time proceeded, the surface of the microwires was gradually covered by microparticles, till they covered the wires along their whole length. Interestingly, microwires with a segmented morphology were also observed. (C) 2011 Elsevier B.V. All rights reserved.