Alginates are a family of natural polysaccharides with promising potential in biomedical applications and tissue regeneration. The design of versatile alginate-based structures or hydrogels and their stability and functionality depend on the polymer’s physicochemical characteristics. The main features of alginate chains that determine their bioactive properties are the molar ratio of mannuronic and glucuronic residues (M/G ratio) and their distribution along the polymer chain (MM-, GG-, and MG blocks). The present study is focused on investigating the influence of the physicochemical characteristics of alginate (sodium salt) on the electrical properties and stability of the dispersion of polymer-coated colloidal particles. Ultrapure and well-characterized biomedical-grade alginate samples were used in the investigation. The dynamics of counterion charge near the vicinity of adsorbed polyion is studied via electrokinetic spectroscopy. The results show that the experimental values of the frequency of relaxation of the electro-optical effect are higher compared to the theoretical ones. Therefore, it was supposed that polarization of the condensed Na+counterions occurs at specific distances according to the molecular structure (G-, M-, or MG-blocks). In the presence of Ca2+, the electro-optical behavior of the particles with adsorbed alginate molecules almost does not depend on the polymer characteristics but was affected by the presence of divalent ions in the polymer layer.