A series of telechelic supramolecular amphiphiles [POSS-Azo(8)@(beta-CD- PDMAEMA)(1 -> 8)] was accomplished by orthogonally coupling the multiarm host polymer beta-cydodextrin poly(dimethylaminoethyl methacrylate) (beta-CD PDMAEMA) with an octatelechelic guest molecule azobenzene modified-polyhedral oligomeric silsesquioxanes (POSS Azo(8)) under different host guest ratios. These telechelic supramolecular amphiphiles possess a rigid core and flexible corona. Increasing the multiarm host polymer coupled onto the rigid POSS core made the molecular architecture tend to be symmetrical and spherical. POSS Azo(8)@[beta-CD PDMAEMA](1 -> 8) could self-assemble into diverse morphologies evolving from spherical micelles, wormlike micelles, and branched aggregates to bowl-shaped vesicles. Distinct from the traditional linear amphiphilic polymers, we discovered that the self-assembly of POSS-Azo(8)@[beta-CD- PDMAEMA](1 -> 8) was dominantly regulated by their molecular architectures instead of hydrophilicity, which has also been verified using computer simulation results.