**Abstract**

Polyimide (PI) is widely employed as winding insulation in high voltage devices, such as extra-high voltage electric reactor and inverter-fed motor. The injection and accumulation of charges on the surface of PI films will lead to electrical field distortion and reduced lifespan of winding insulation, especially for the operation environment of high temperature and high voltage. This chapter focuses on effects of surface molecular modification and nanoparticles on dynamic characteristics of surface charge and space charge of pure PI films, including three sections. The effect of molecular structure on the surface charge dynamics of PI films was studied firstly. The chapter investigated that how molecular structure affects surface charge of polyimide nanocomposite films. Furthermore, the effect of surface molecular modification on space charge characteristics of multilayer PI films was researched. The results illustrate that surface molecular modification and nanoparticles can comprehensively suppress space charge accumulation and improve dielectric property.

**Keywords:** polyimide, surface molecular modification, nanoparticles, surface charge, space charge
