The structural and functional properties of two different pea water-soluble polysaccharides, a high methyl-esterified (HM-SPPS; degree of methyl esterification (DMe): 71.0 %) and low methyl-esterified SPPS (LM-SPPS; DMe: 25.2 %) were investigated. The two extracts did not vary in composition and showed a weight average molecular mass of about 1,000 kDa, as measured by size exclusion chromatography equipped with a multi-angle light scattering detector. Both HM-SPPS and LM-SPPS had similar sugar compositions, with arabinose 42.2–47.1 %, glucose 26.6–31.0 %, and galacturonic acid 17.5–18.0 %, as their main sugars. Their charge varied as a function of pH. The molecular structure was observed by a scanning probe microscope and showed a straight chain structure with small branches. The structure was similar to that already reported for polysaccharides from kidney bean. SPPS molecules interact with acidified milk protein particles at pH < 4.4. There were differences between the two SPPS. LM-SPPS could stabilize a model acidified milk dispersion with minimal aggregation between pH 3.6–4.4, while HM-SPPS showed the presence of bridging flocculation caused by polysaccharide's entanglements.