Multi-scale structural interactions of the arrowhead starch-linoleic/stearic acid complexes under different durations (20, 40 & 60 min) of dual-frequency power ultrasound (DFPU, 20/40 kHz) and their underlying mechanisms were discussed. Differential scanning calorimetry and X-ray diffraction (XRD) revealed V6 type (V6-I, II) crystalline structure for ultrasonically-treated arrowhead starch-linoleic acid (UTAS-LA) complexes. An increased degree of short-range molecular order as IR ratios of 1045/1022 cm⁻¹ was evident from the FTIR results. The complexing index (CI) values of the complexes were greater than 65%, and the highest CI values of 83.04% and 81.26% were found in the case of UTAS-LA40 and UTAS-LA60, respectively. SEM results showed that LA-complexes had a sponge-like structure with smooth surfaces, while the SA-complexes exhibited flaky structures with irregular shapes and rough surfaces. The V-type complexes exhibited a higher digestion resistance than native AS and un-sonicated AS-LA/SA complexes due to partial RDS convention to RS.