Hydrogels obtained by acidification with glucono-δ-lactone (GDL), starting from nanoemulsions formulated with different concentrations of sodium caseinate (1–4 wt%) or 4 wt% sodium caseinate and sucrose (2–8 wt%), were prepared with the aim of quantifying structural parameters of both, initial nanoemulsions and hydrogels after 2.5 h of GDL addition, using the Guinier-Porod (GP) or the generalized GP models. Gelation process was followed by performing in situ temperature-controlled X-ray small angle scattering experiments (SAXS) using synchrotron radiation. In nanoemulsions, the calculated radius of gyration for oil nanodroplets (Rgoil) decreased with increasing protein concentration and for the 4 wt% protein nanoemulsion, with increasing sucrose content. Calculated values of Rgoil were validated correlating them with experimental Z-average values as measured by dynamic light scattering (DLS). For hydrogels, radii of gyration for the sphere equivalent to the hydrogel scattering object (Rgsph) were close to 3 nm while correlation distances among building blocks (Rg2) were dependent on formulation. They increased with increasing contents of sodium caseinate and sucrose. Rg2 parameter linearly correlated with hydrogel strength (G’∞): a more connected nanostructure led to a stronger hydrogel.