In this study, polyhedral oligomeric silsesquioxane (POSS) end-capped amphiphilic POSS-block-poly (N, Ndimethylaminoethyl methacrylate)-block-poly (methyl methacrylate) (POSS-b-PDMAEMA-b-PMMA) was synthesized by a two-step atom transfer radical polymerization (ATRP), and its assembly morphologies in different solvents were investigated. POSS-b-PDMAEMA-b-PMMA micelles were used to encapsulate tetraphenylethene (TPE) to study the effect of selfassembly shape on the fluorescent intensity and bioimaging of TPE. Spherical polymeric micelles enhanced the fluorescent intensity of TPE more than rod-like and necklace-like polymeric micelles while rod-like polymeric micelles had better intracellular uptake than spherical polymeric micelles.