Both low-dimensional bar-coded metal oxide layers, which exhibit molecular hinging, and free-standing organic nanostructures can be obtained from unique nanofibers of vanadium oxide (VO(x)). The nanofibers are successfully synthesized by a simple chemical route using an ethanolic solution of vanadium pentoxide xerogel and dodecanethiol resulting in a double bilayered laminar turbostratic structure. The formation of vanadium oxide nanofibers is observed after hydrothermal treatment of the thiol-intercalated xerogel, resulting in typical lengths in the range 2-6 microm and widths of about 50-500 nm. We observe concomitant hinging of the flexible nanofiber lamina at periodic hinge points in the final product on both the nanoscale and molecular level. Bar-coded nanofibers comprise alternating segments of organic-inorganic (thiols-VO(x)) material and are amenable to segmented, localized metal nanoparticle docking. Under certain conditions free-standing bilayered organic nanostructures are realized.