Triboelectric generator is attracting much attention as a power source of electronics application. Electromotive force induced by rubbing is a key for triboelectric generator. From dielectric physics point of view, there are two microscopic origins for electromotive force, i.e., electronic charge displacement and dipolar rotation. A new way for evaluating these two origins is an urgent task. We have been developing an optical second-harmonic generation (SHG) technique as a tool for probing charge displacement and dipolar alignment, selectively, by utilizing wavelength dependent response of SHG to the two origins. In this paper, an experimental way that identifies polarity of electronic charge displacement, i.e., positive charge and negative charge, is proposed. Results showed that the use of local oscillator makes it possible to identify the polarity of charges by means of SHG. As an example, positive and negative charge distribution created by rubbing polyimide surface is illustrated.