The unusual properties of nanocomposites are commonly explained by the structure of their interphase. Therefore, these nanoscale interphase regions need to be precisely characterized; however, the existing high resolution experimental methods have not been reliably adapted to this purpose. Electrostatic force microscopy (EFM) represents a promising technique to fulfill this objective, although no complete and accurate interphase study has been published to date and EFM signal interpretation is not straightforward. The aim of this work was to establish accurate EFM signal analysis methods to investigate interphases in nanodielectrics using three experimental protocols. Samples with well-known, controllable properties were designed and synthesized to electrostatically model nanodielectrics with the aim of "calibrating" the EFM technique for future interphase studies. EFM was demonstrated to be able to discriminate between alumina and silicon dioxide interphase layers of 50 and 100 nm thickness deposited over polystyrene spheres and different types of matrix materials. Consistent permittivity values were also deduced by comparison of experimental data and numerical simulations, as well as the interface state of silicone dioxide layers.