This paper presents a novel aerogel-based Triboelectric Nanogenerator (TENG) which shows a superior performance for energy harvesting and sensing applications. Polyimide-based aerogel film with varying open-cell content level is developed to be used as the main contact material for the TENG. The fabricated aerogel film is fully characterized to reveal the chemical and mechanical properties of the developed material. It is shown the use of Polyimide aerogel film remarkably enhances the performance of the TENG compared to a TENG with fully dense Polyimide layer with no porosity. This enhancement is due to the increase on the effective surface area, charge generation inside the open-cells of the aerogel, and increase on the relative capacitance of the TENG device. The effect of varying porosity from zero to 70% of open-cell content reveals that the aerogel film with 50% shows the highest performance where the peak open-circuit voltage of 40V and peak short-circuit current of 5 μA are obtained. These values are higher than those of the TENG with simple Polyimide layer with an order of magnitude. Finally, the performance of proposed TENG under resistive loads and capacitors are tested. Thus, this work presents an effective method for high performance TENG.