The colloidal properties of Salmonella promote its adhesion to the oil–water interface in fatty food emulsions, hindering separation from the aqueous phase and reducing the sensitivity of rapid detection assays. There have been studies that utilized α-amylase to hydrolyze starch to enhance the detection of Salmonella in ground beef. However, the interfacial behavior of enzyme-modified starch and its relationship with bacterial distribution in oil–water systems is unclear. Based on this background, an enzyme-modified soluble starch (E-SS) was prepared that can effectively recover Salmonella from meat samples. Furthermore, this study examined the molecular structure of E-SS and its regulatory effect on Salmonella distribution in oil–water systems. Compared with native soluble starch (SS), E-SS exhibited a smaller molecular weight distribution (Mw = 3.184 × 103 ± 5.776