The triboelectric nanogenerator (TENG) has enormous application prospects and research value in energy collection due to its small size, simple structure, and ability to convert mechanical energy into electrical energy output. The microstructure of TENG’s friction layer has a significant impact on its output performance. We, herein, propose a surface modification method by replicating the surface morphology of sandpaper to construct microstructure on the surface of chitosan film or by constructing porous structure using electrospinning technology. Thanks to the significant increase in the effective contact area between the two friction materials, the output performance of the vertical contact-separation TENG with chitosan (Fluorinated ethylene propylene) film being used as a friction positive (negative) material is greatly enhanced. This TENG also exhibits its sensitivity in perceiving human movements and has good power supply capabilities. Our results indicate that surface modification of the friction materials is a facile strategy to boost the performance of TENG.