In this study, we investigated the synthesis of water-soluble amylose-PPV composites obtained by polymerization of the PPV monomer in an aqueous solution of amylose. The amylose-PPV composites were soluble in aqueous DMSO. 1H NMR spectra of the composite showed that the interior polymer consisted of the PPV units and a small amount of the precursor units. The composite showed the absorption and fluorescence being characteristic of PPV. In the CD spectra, the composite exhibited Cotton effects at around the absorption region of the PPV units, which suggests that the PPV units adopt a chiral twisted conformation. These results as well as other analytical ones such as SEC and XRD support the encapsulated structure of the PPV polymer in the amylose tube.