Dendron-like poly(gamma-benzyl-L-glutamate)/linear poly(epsilon-caprolactone)/dendron-like poly(gamma-benzyl-L-glutamate) triblock copolymers having 2(m + 1) PBLG branches (denoted as PBLG-Dm-PCL-Dm-PBLG, m = 0, 1, 2, and 3) were for the first time synthesized by utilizing ring-opening polymerization (ROP) and click chemistry. The bifunctional azide-terminated PCL (N-3-PCL-N-3) was click conjugated with propargyl focal point PAMAM-typed dendrons Dm to generate Dm-PCL-Dm, which was then used as macroinitiator for the ROP of BLG-NCA monomer to produce the targeted PBLG-Dm-PCL-Dm-PBLG triblock copolymers. Their molecular structures and physical properties were characterized in detail by FTIR, NMR, gel permeation chromatography, differential scanning calorimetry, and wide angle X-ray diffraction (WAXD). The crystallinity of the central PCL segment within these copolymers is increasingly suppressed by the flanking PBLG wedges, whereas the PBLG segments gradually changed from a beta-sheet conformation to an alpha-helix conformation with the increasing PBLG branches. These triblock copolymers formed thermoreversible organogels in toluene, and the dendritic topology of PBLG wedges controlled their critical gelation concentrations. The self-assembled structure of organogels was further characterized by means of transmission electron microscopy, WAXD, and small-angle X-ray scattering. The fibers with flat ribbon morphology were clearly shown, and the gelation occurred through a self-assembled nanoribbon mechanism. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 709-718, 2010