Contact electrification between two different materials is one of the oldest fields of study in solid-state physics. Here, we introduced an innovative system based on optical electric-field-induced second harmonic generation (EFI-SHG) technique that can directly monitor the dynamic performance of the contact electrification on the surface of polyimide film. After the contact, the EFI-SHG system visualized briefly three relaxations of the tribo-induced charges on the surface of a polyimide film, a fast relaxation within 3 min followed by two much slower relaxations, which were possibly related to different charge diffusion routes. The contact electrification under several special experimental conditions (wind, water and steam) was studied to demonstrate the high flexibility and material selectivity of the EFI-SHG. The EFI-SHG studies confirmed the motion of the water can remove the surface charge, while the appearance and the evaporation of a thin water layer cannot enhance the charge diffusion. We anticipate that this experimental technique will find a variety of applications in the field of contact electrification and the development of the recently invented triboelectric nano generator.