Amylose can be synthesized with phosphorylase (EC 2.4.1.1) by using malto-oligosaccharides as primers. In this context, the glucose-1-phosphate (G-1-P) units are consumed through the polymerization process. In this study, we investigated the use of amylopectin as a primer for the synthesis of a novel starch. The obtained starch was characterized by dynamic light scattering, small-angle X-ray scattering (SAXS) and X-ray diffraction. The SAXS results were well represented by the star-polymer model scattering function. According to these results, we think that the amylopectin chain elongation was implied, and the transformation of crysralline type of amylopectin was observed by X-ray diffraction.