Recently triboelectric nanogenerators (TENGs) have attracted huge interest because of their flexibility to harvest wasted mechanical energy. However, triboelectrification is a well-known phenomenon for centuries, the underlying physics behind it is still under debate, so a comprehensive study on triboelectrification is needed. Herein, effects of polyvinylidene fluoride (PVDF) friction layers thickness, contact area and porosity on TENGs performance were investigated. Results showed that increasing surface area or decreasing thickness of friction layer positively affected the performance of TENG. This is mainly attributed to improvement of PVDF charge density. Then, for further enhancement of TENGs performance, electroactive phase content of PVDF enhanced using different fabrication methods such as supercritical CO2 processing, non-isothermal crystallization, electro-poling and electrospinning. The results confirmed increasing in PVDF electroactive phase content positively affected triboelectric properties. Consequently, by fabrication of chitin-PVDF electrospun film the average of voltage and current density increased to 72.8 V and 6.47 mA/m², respectively.