This Account describes our approach to single polymer science in which we use end-grafted polysilane. Single polymer science, by our definition, involves isolating and observing a single polymer chain and extracting its physical properties at the single molecule level. For this purpose, we developed the end-graft technique, which is a method for fixing a polymer terminus on a solid surface by forming a chemical bond between them. We applied this technique to polysilane, a semiconducting polymer with a one-dimensional silicon-catenated backbone. Our recent experimental achievements are reviewed, which include direct observations of polysilane single-molecular structures by atomic force microscopy, the formation of unique supramolecular structures, and the observation of temperature- and solvent-dependent UV absorption spectra that are characteristic of isolated polysilane chains end-grafted on a solid surface.