As the main source of energy for human beings, starch is widely present in people's daily diet. However, due to its high content of rapidly digestive starch, it can cause a rapid increase in blood glucose after consumption, which is harmful to the human body. In the current study, the complexes made from edible rose polyphenols (ERPs) and three starches (corn, potato and pea) with different typical crystalline were prepared separately by multi-frequency power ultrasound (MFPU). The MFPU includes single-frequency modes of 40, 60 kHz and dual-frequency of 40 and 60 kHz in sequential and simultaneous mode. The results of the amount of complexes showed that ultrasound could promote the formation of polyphenol-starch complexes for all the three starches and the amount of ERPs in complexes depended on the ultrasonic parameters including treatment power, time and frequency. Infrared spectroscopy and X-ray diffraction indicated that ERPs with or without ultrasound could interact with the three starches through non-covalent bonds to form non-V-type complexes. Scanning electron microscopy showed that the shape of starches changed obviously from round/oval to angular and the surface of the starches were no longer smooth and appeared obvious pits, indicating that the ultrasonic field destroyed the structure of starches. In addition, compared to the control group, the in vitro digestibility study with 40/60 kHz sonication revealed that ultrasonic treatment greatly improved the digestive properties of the polyphenol-starch complexes by significantly increasing the content of resistant starch (20.31%, 17.27% and 14.98%) in the three starches. Furthermore, the viscosity properties of the three starches were all decreased after ERPs addition and the effect was enhanced by ultrasound both for single- and dual-frequency. In conclusion, ultrasound can be used as an effective method for preparing ERPs-starch complexes to develop high value-added products and low glycemic index (GI) foods.