Three different self-assembled nanostructures, i.e., lamellar (Lam), hexagonally close-packed cylinder (Hex), and body-centered cubic (BCC), have been obtained from ABA triblock (MH-b-PCL-b-MH) and A(2)B star-branched copolymers ((MH)(2)-b-PCL) consisting of maltoheptaose (MH, as the A block) and polycaprolactone (PCL, as the B block). MH-b-PCL-b-MH and(MH)(2)-b-PCL were synthesized by the click reaction of the alpha,omega-diazido and alpha,alpha-diazido end-functionalized PCLs with N-maltoheptaosyl-3-acetamido-1-propyne in high yields. The self-assembled nanostructures of the block copolymers (BCPs) in bulk were investigated as a function of temperature by time-resolved small-angle X-ray scattering using a synchrotron light source. The SAXS analysis revealed that the obtained BCPs exhibited microphase-separated structures with the domain-spacing of 10.4-21.0 nm. MH-b-PCL-b-MH (the MH volume fraction (phi(MH)) of 0.28 and 0.15) exhibited a hexagonally close-packed cylinder (Hex) at below ca. 230 degrees C, and the self-assembling behavior of MH-b-PCL-b-MH was essentially the same as that of the diblock counterpart, MH-b-PCL, having comparable phi(MH) values. The lamellar (Lam) morphology, which was unattainable from the corresponding linear counterparts, was observed from (MH)(2)-b-PCL (phi(MH) = 0.27 and 0.16). Furthermore, the microphase transitions from the Hex into the body-centered cubic sphere and the Lam into the Hex were observed upon the thermal caramelization of the MH block.