The aim of this study was to prepare a supporting carrier, namely highly branched corn starch (HBCS), and to investigate its encapsulation property with ascorbic acid (AA). High amylose corn starch was converted into HBCS via dual enzymatic modification by successively using α-amylase and glycogen branching enzyme. The results showed that the ratio of α-1, 6 linkage of HBCS increased by 1.93%, and a short-to-medium chain length distribution with a compact branched conformation was formed, which suggested HBCS could be a potential highly branched carrier. The HBCS-AA inclusion complex was formed as confirmed by differential scanning calorimetry. The release of AA conformed to the pseudo-Fickian diffusion mechanism and followed the first-order kinetics. Meanwhile, the photostability and thermostability of the embedded AA were moderately enhanced. These findings suggest that HBCS provides new insights into the preparation of wall materials and can be potentially used to deliver AA into food systems.