Short oligoguluronates, oligoG’s, are reported to affect the ionotropic gelation of alginates both with respect to altered gelation kinetics and elastic properties of the resulting gels. The local structure of Ca2+ induced changes in oligoguluronates and blends of oligoguluronates and alginates was determined by small angle X-ray scattering (SAXS). Calcium was introduced in the aqueous polysaccharide solutions by in situ release of Ca2+ from Ca-EGTA. The scattering profiles of the Ca2+-induced structures in the alginate–oligoG blends were accounted for by a two-component broken rod-like model, also with an additional term representing structural inhomogeneity by a Debye-Bueche term. Adding oligoG to the alginate yields an increase in the largest cross-sectional radius in the region of fractional Ca2+ saturation of α-l-GulA units from 0.5 to 1. The time-lapse characterization during the Ca-induced changes in the alginate-oligoG blends shows that oligoG delays the emergence of the more extensive laterally aggregated junction zones.