Electrostatic processes are argued to be of fundamental importance in understanding the particle dynamics and complex dusty plasma environment over airless bodies—the Moon has been of particular interest. Based on the theory of electrostatic charge fluctuation corresponding to the photoemission current, the fundamental problem of dust detachment from the lunar surface is addressed. By applying the charge fluctuation at the microscopic scale, we have quantified the magnitude of fluctuating charge density over the sunlit lunar surface and illustrated that it could induce a sufficient electric field to overcome the dust–surface adhesive van der Waals bonding through the electrostatic Coulomb repulsion. The analysis takes into account the dynamic equations for the statistical variables, viz., the mean charge and the variance, corresponding to the charge distribution over the microscopic spots exposed to the solar radiation. The photoemission under the influence of extreme ultraviolet Lyman α radiation in the solar spectrum and subsequent collection of the emitted photoelectrons are accounted for as the dominant charging processes of the lunar surface. Based on analysis and calculations, the fluctuating charge is illustrated to be a significant function of the spot size, which may induce significantly high electric field fluctuations locally. As an illustrative example, it is shown that one square micrometer spot may acquire ∼15 electronic charges and might induce a local electric field equivalent to ∼10 kV/m, which can support the detachment of the submicrometer dust particles from the lunar surface.