The effect of several blending procedures between Ascophyllum nodosum seaweed flour (AF) and corn starch (CS) on the interactions between polyphenols and starch was studied in this paper. These methods comprised the blending of AF with native starch (NT) with previously gelled starch gel (GL) and promoting the gelling of corn starch in the presence of AF (CGL). Different AF–CS (g/g) ratios (from 1:0.5 to 1:25) were studied. The liquid phase was chemically characterized by polyphenols (TPC) and carbohydrates content. The antioxidant activity of the liquid phase after achieving the solid–liquid equilibrium was determined by DPPH, ABTS, and FRAP methods. The solid phase was characterized by FT-IR and SEM techniques. The Halsey model successfully fitted the equilibrium TPC in liquid and polyphenols adsorbed/retained by the solid phase of tested systems. NT samples showed lower polyphenols sorption than gelled samples. The differences found between samples obtained with GL and CGL methods suggested different interactions between polyphenols and starch. Specifically, physisorption is predominant in the case of the GL method, and molecular trapping of polyphenols in the starch gel structure is relevant for the CGL method. Results allowed us to determine the enhancement of the retention of polyphenols to achieve starchy foods with high bioactivity.