Fumed silica Cab-O-Sil HS-5 grafted with 3-aminopropyldimethylsilyl (APDMS), butyldimethylsilyl (BDMS), octadecyldimethylsilyl (ODDMS), and trimethylsilyl (TMS) groups of different concentrations were studied using photon correlation spectroscopy, electrophoresis, potentiometric titration, and nitrogen adsorption methods. Calculations of both electrophoretic mobility and ζ potential were performed taking into consideration the topological structure of “porous” aggregates of primary particles of fumed silica using two different approaches. Changes in surface charge density and the textural, aggregative, and electrophoretic characteristics of modified silicas depend on the type of grafted OSC, its chain length, polarity, and surface concentration. Particle swarms of initial and modified silicas in aqueous suspension are typically characterized by bimodal size distributions between 20 and 300 nm (aggregates) and 1–3 μm (agglomerates of aggregates). The difference between parameter values computed according to the Smoluchowski theory and improved approaches increases with increasing pH and is concordant for both mobility and ζ potential.