The chemical and electrostatic interactions at mineral-water interfaces are of fundamental importance in many geochemical, materials science, and technological processes; however, the effects of particle size at the nanoscale on these interactions are poorly known. Therefore, comprehensive experimental and characterization studies were completed, to begin to assess the effects of particle size on the surface reactivity and charging of metal-oxide nanoparticles in aqueous solutions. Commercially available crystalline anatase (TiO2) particles were characterized using neutron and X-ray small-angle scattering, electron microscopy, and laser diffraction techniques. The 4 nm primary nanoparticles were found to exist almost exclusively in a hierarchy of agglomerated structures. Potentiometric and electrophoretic mobility titrations were completed in NaCl media at ionic strengths from (0.005 to 0.3) mol/kg, and 25°C, with these two experimental techniques matched as closely as the different procedures permitted. The pH of zero net proton charge (pHznpc, from potentiometric titration) and isoelectric point pH value (pHiep, from electrophoretic mobility titrations) were both in near perfect agreement (6.85 ± 0.02). At high ionic strengths the apparent pHznpc value was offset slightly toward lower pH values, which suggests some specific adsorption of the Na+ electrolyte ions. Proton-induced surface charge curves of nanocrystalline anatase were very similar to those of larger rutile crystallites when expressed relative to their respective pHznpc values, indicating that the development of positive and negative surface charge away from the pHznpc for nanocrystalline anatase is similar to that of larger TiO2 crystallites.