An alkylated cage silsesquioxane (1), targeting for a new class of bottom-up-type fabricating materials, was successfully synthesized, and its self-assembled structure is described and discussed herein. Through this, it was found that the intermolecular interaction of long alkyl chains of 1 could be manipulated by thermal annealing to form a long-range straight ordered hierarchical lamellar structure with a periodicity of around 5 nm. Subsequent transmission electron microscopy (TEM) clearly identified polyhedral oligomeric silsesquioxane (POSS) molecules of 1 arranged in a highly ordered fashion, with a "head-to-head" type bilayered structure. The observation of a sublayer structure measuring approximately 0.4 nm in width was attributed to the highly regular packing of isobutyl groups in POSS molecules identified by TEM analysis. Moreover, the formation of a long-range straight structure with sharp interfacial boundaries, which is difficult to achieve with traditional diblock copolymers, is considered to be of significant importance to developing new practical applications of self-assembled nanostructures.