Cycloamylose (CA) exhibits difference,; in geometry and greater colloidal stability compared with amylose. Here we report the synthesis of a cationic CA derivative and its application for gene delivery Cationic CA (catCA) and cationic amylose (catAmy) were synthesized by introducing spermine groups The interactions between catCA or catAmy with plasmid DNA encoding firefly luciferase was examined by gel electrophoresis, dynamic light scattering, and transmission electron microscopy. Activity as I gene delivery system was evaluated by flow cytometry and luciferase assays. CatCA formed I condensed pDNA complex (similar to 250 nm in size). The catCA complex showed enhanced cellular uptake and greater transfection efficiency than the catAmy complex. Hemolysis by membrane destabilization and the effects of hydroxychloroquine on transfection ability suggest that the formation of a supramolecular complex with CA is important for high transfection activity These results suggested that CA can be used its new polysaccharide-based biomaterials.