Thin films of vanadium oxides were grown on fused quartz by metalorganic chemical vapor deposition using vanadyl acetylacetonate as the precursor. Growth at temperatures ⩾560 °C results in composites of strongly (00l)-oriented V2O5 and V6O13. The dominant phase of the film changes from V2O5 to V6O13, and back to V2O5, as the growth temperature is raised from 560 to 570 °C, then to 580 °C, as evidenced by x-ray diffraction and Rutherford backscattering analyses. This reentrant-type growth trend was interpreted on the basis of the small difference in the free energy of formation of V2O5 and V6O13 and the presence of metal–oxygen bonds in the precursor. In contrast with single-crystalline V6O13, the film predominantly composed of highly oriented single-crystalline platelets of V6O13 did not undergo the semiconductor–metal transition at −123° K, despite the connectivity being well above the percolation threshold. Instead, a semiconductor-to-semiconductor transition was observed in this film, which is explained in terms of the observed relaxation of the edges of all the platelets of metallic V6O13 to semiconducting V2O5.