The effects of molecular weight (MW) and degree of esterification (DE) of soluble soybean polysaccharide (SSPS) on the stability of casein under acidic conditions were investigated. The ability of SSPS to stabilize casein was characterized by the content of SSPS–casein complex, the LUMiSizer instability index, average particle size, zeta potential, and storage experiments. The long-term storage stability of the mixtures was related to their ability to combine casein and the stability of the complexes. At the same DE, SSPSs with medium MW formed more complexes with casein than SSPSs with high or low MW; and at the same MW, SSPSs with medium or low DE formed more complexes than SPSSs with high DE. In addition, SSPSs with higher MW had a better stabilizing behavior due to the large steric repulsion between complexes. SSPSs with high MW and low DE showed the best ability to stabilize casein under acid conditions.