Unique bismuth telluridenanostructures, tri-wing nanoribbons, are controllably synthesized on a large scale by a facile one-pot hydrothermal method. The length of the nanoribbon is up to tens of micrometres, and the wing of the nanoribbon is very thin with an average thickness of about 20 nm. During the synthesis process, tri-wing Tenanoribbons are first formed and act as the template, highly crystalline tri-wing Bi2Te3nanoribbons are then obtained through a surface-directing diffusion process. An elaborate TEM study reveals a quasi-periodic rough surface with sequential (15) and (05) planes along the Bi2Te3nanoribbon, which is ascribed to the coherent growth of Bi2Te3 crystals during the surface-directing diffusion process. The successful synthesis of Bi2Te3nanoribbons with rough surfaces opens up the opportunities of developing high performance nanoscale thermoelectrics as well as studying the surface state of Bi2Te3nanoribbons as potential topological insulators.