Waxy and non-waxy rice starches from japonica type Korean rice varieties were esterified with different levels of octenyl succinic anhydride (OSA), and the molecular structure of amylopectin (AP), digestibility, and emulsion stability were investigated. As OSA levels increased, the degree of substitution, granule size, peak and final viscosities, emulsion stability, and short chain of AP increased. However, the gelatinization temperature and enthalpy, and digestibility decreased. All OSA esterified starches showed a new band at 1723 cm−1, but maintained A-type crystallinity. The DP6-12 of AP in waxy rice starch (WRS) was higher than that in non-waxy rice starch (NRS) with increasing OSA levels. Because the amylose and long chain of AP accessed easily with OSA groups, the digestibility of NRS was lower than that of WRS. The emulsion stability was higher in WRS than in NRS. From the above results, it is suggested that amylose should have a higher affinity with OSA esterification than AP and that the emulsion stability should increase in WRS, but the digestibility should decrease in NRS after OSA modification.