The nano-particles in colloidal dispersions usually carry an electrical charge and have an electrical double layer associated with their surfaces, however, while remaining electrically neutral overall. Under the effect of an external electric field, the electrical double layer is deformed or in other words, the suspension is polarized. The mechanism of electrochemical polarization is partially dependent on the surface charge and the size of particles. It is known that properties of nano-particles in suspensions may affect the colloids' electrical-impedance spectroscopic properties, e.g., the complex impedance, complex permittivity, complex conductivity, relaxation frequency, and phase angle. However, reports on colloids' electrical-impedance spectroscopic properties are very limited in the current literature. In this paper a simple system, aqueous silica suspensions, was studied using electrical impedance spectroscopy (EIS). A series of experiments were designed to reveal the effect of particle size on the electrical impedance spectra of silica suspensions. The size effect was studied on silica suspensions with the same concentration (10.0 wt%) but different principle particle size (12 nm, 35 nm, 70 nm, 90 nm and 220 nm). The EIS results show that the relaxation frequency decreased with increasing of particle size. This tendency is explained by the polarization effect of electrical double layer and two dispersion mechanisms were analysed in this study. The results provide supportive information for on-line characterisation of nano-particles using electrical impedance spectroscopy.