Finite element simulations for detecting the dielectric permittivity of planar nanoscale dielectrics by electrostatic probe are performed to explore the microprobe technology of characterizing nanomaterials. The electrostatic force produced by the polarization of nanoscale dielectrics is analyzed by a capacitance gradient between the probe and nano-sample in an electrostatic detection system, in which sample thickness is varied in the range of 1 nm–10 μm, the width (diameter) encompasses from 100 nm to 10 μm, the tilt angle of probe alters between 0° and 20°, and the relative dielectric constant covers 2–1000 to represent a majority of dielectric materials. For dielectric thin films with infinite lateral dimension, the critical diameter is determined, not only by the geometric shape and tilt angle of detecting probe, but also by the thickness of the tested nanofilm. Meanwhile, for the thickness greater than 100 nm, the critical diameter is almost independent on the probe geometry while being primarily dominated by the thickness and dielectric permittivity of nanomaterials, which approximately complies a variation as exponential functions. For nanofilms with a plane size which can be regarded as infinite, a pertaining analytical formalism is established and verified for the film thickness in an ultrathin limit of 10–100 nm, with the probe axis being perpendicular and tilt to film plane, respectively. The present research suggests a general testing scheme for characterizing flat, nanoscale, dielectric materials on metal substrates by means of electrostatic microscopy, which can realize an accurate quantitative analysis of dielectric permittivity.