Abstract Structure of tapioca starch (raw) was reorganized under annealing treatment during 12-72 h. Then, raw and annealed starches were modified by Argon-plasma treatment (P sample) under atmospheric pressure at constant parameters (137.5 V, 1 A, 10 min). Treated samples were characterized degree of cross-linking (DCL), degree of relative crystallinity (DRC), and in vitro digestibility using Fourier Transform Infrared Spectroscopy, X-ray difractometry, respectively. Results showed that DCL increased during both annealing and plasma treatments. Besides, DRC of annealed starches was higher than that of raw, but it was slightly reduced under plasma treatment. Furthermore, A-type crystal pattern of samples was remained during treatments. Annealing resulted in a significant increase of resistant starch (RS) fraction and further plasma treatment continuously enhanced RS content from 30.5% of raw starch to around 71.0% of 72h-P (dual treated) sample. After boiling, RS fraction of the starch was (decreased by 4%) 67%. Thus, dual treatment (annealing and plasma) is a novel and potent method of both RS and boiled RS production.