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The preparation of macroscopic fibers of oriented vanadium oxide ribbons and their application as highly sensitive alcohol microsensors were discussed. These fibers showed anisotropic mechanical properties in terms of both transversal flexibility and the quasi-absence of longitudinal plasticity. The vanadium oxide fibers also showed textural anisotropy at higher scales, as revealed by optical microscopy between crossed polarizers. Transmission electron microscopy (TEM) observations revealed that the nanoscale ribbon subunits were preferentially organized parallel to the main axis of the macroscopic fiber.