This research proposed a simple ionic embedded method to improve electrical output performance by adding surface charges of cationic chitosan (CS) biopolymer for compatible utilization of the triboelectric nanogenerator (TENG). By simply embedding cationic salts, the TENG performance was enhanced by over four times more than that with pristine CS. Moreover, by modifying roughness on the film surface, the optimized condition of R-CS/3 %CaCl2 reached the highest VOC and ISC of ~149 V and ~15 μA, respectively, thus exceeding the output from pristine R-CS TENG by four- and three times of ⁓38 V and ⁓5.1 μA. The maximum power output of 400 μW/cm2 can be observed at the 10 MΩ external load resistance. Finally, by integrating an automatic self-charge pumping (ASCP) module, the ASCP/CS-TENG provided highly efficient VOC and ISC output power by over 1.3 times more than the R-CS/3 %CaCl2 TENG and could light up 72 light emitting diodes (LEDs) easily.