To ameliorate the limitations of corn starch (CS) processing, Radix Paeoniae Alba polysaccharide (RPAP) was used to modulate the physicochemical and digestive properties of CS. The main purpose of this paper is to investigate the effects of RPAP on the pasting, rheological, thermal, structural, and digestive properties of CS. The results show that the addition of RPAP could increase the peak viscosity and final viscosity of CS gel, and RPAP could increase the apparent viscosity, storage modulus, loss modulus, hardness, and strength of CS gel, implying that RPAP can effectively improve the pasting and viscoelasticity properties of CS. Moreover, RPAP could be bound to CS through non-covalent interaction, and RPAP could improve the relative crystallinity and thermal stability, whereas decreased the spin relaxation time (T