From the structure point of view, there are a number of ways of tiling a carbon sheet with different polygons, resulting in prospects of tailoring electronic structures of low-dimensional carbon nanomaterials. However, up to now, the experimental fabrication of such structures embedded with periodic nonhexagon carbon polygons, especially ones with more than three kinds, is still very challenging, leaving their potential properties unexplored. Here we report the bottom-up synthesis of a nanoribbon composed of 4-5-6-8-membered rings via lateral fusion of polyfluorene chains on Au(111). Scanning probe microscopy unequivocally determines both the geometric structure and the electronic properties of such a nanoribbon, revealing its semiconducting property with a bandgap of ∼1.4 eV on Au(111). We expect that this work could be helpful for designing and synthesizing complicated carbon nanoribbons.