In general, the complexation and gelation behavior between biocompatible poly(epsilon-caprolactone) (PCL) derivatives and -cyclodextrin (-CD) is extensively studied in water, but not in organic solvents. In this article, the complexation and gelation behavior between -CD and multi-arm polymer -cyclodextrin-PCL (-CD-PCL) with a unique jellyfish-like structure are thoroughly investigated in organic solvent N,N-dimethylformamide and a new heat-induced organogel is obtained. However, PCL linear polymers cannot form organogels under the same condition. The complexation is characterized by rheological measurements, DSC, XRD, and SEM. The SEM images reveal that the complexes between -CD-PCL and -CD present a novel topological helix porous structure which is distinctly different from the lamellar structure formed by PCL linear polymers and -CD, suggesting the unique jellyfish-like structure of -CD-PCL is crucial for the formation of the organogels. This research may provide insight into constructing new supramolecular organogels and potential for designing new functional biomaterials. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1598-1606