High-yield synthesis of bamboo-raft-like single-crystalline selenium superstructures has been realized for the first time via a facile solvothermal approach by reducing SeO2 with ethylene alcohol in the presence of cellulose acetate. The formation of a raftlike superstructure with various forms is strongly dependent on the temperature, amount of cellulose acetate, reaction time, and even preheating treatment. The suitable amount of cellulose acetate is essential for the formation of elegant and uniform raft Se. The morphology, microstructure, optical properties, and chemical compositions of bamboo-raft-like selenium were characterized using various techniques (X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy (TEM), high-resolution (HR) TEM, X-ray photoelectron spectroscopy, UV-vis spectroscopy, FTIR spectroscopy, and Raman spectroscopy). A possible growth mechanism has been proposed. Such special superstructures could provide a useful precursor for potential applications.