Interest in amylose and its hybrids has grown over many decades, and a great deal of work has been devoted to developing methods for designing functional amylose hybrids. In this context, phosphorylase‐catalyzed polymerization shows considerable promise as a tool for preparing diverse amylose hybrids. Recently, advances have been made in the chemoenzymatic synthesis and characterization of amylose‐block‐polymers, amylose‐graft‐polymers, amylose‐modified surfaces, hetero‐oligosaccharides, and cellodextrin hybrids. Many of these saccharides provide clear opportunities for advances in biomaterials because of their biocompatibility and biodegradability. Important developments in bioapplications of amylose hybrids have also been made, and such newly developed amylose hybrids will help promote the development of new generations of glyco materials. WIREs Nanomed Nanobiotechnol 2017, 9:e1423. doi: 10.1002/wnan.1423For further resources related to this article, please visit the WIREs website.