The pursuit of enhancing the performance of triboelectric nanogenerators (TENGs) has led to the exploration of new materials with efficient charge-generating capabilities. Herein, we propose benzylpenicillin sodium salt (b-PEN) as a candidate biomaterial for the tribopositive layer owing to its superior electron-donating capability via the lone pairs of electrons on its sulfur atom, carbonyl, and amino functional groups. The proposed b-PEN TENG device exhibits promising electrical performance with an open-circuit voltage of 185 V, a short-circuit current of 4.52 µA, and a maximum power density of 72 µW/cm2 under force applied by a pneumatic air cylinder at 5 Hz. The biomechanical energy-harvesting capabilities of the b-PEN TENG device are demonstrated by actuating it with finger, hand, and foot movements. Moreover, the proposed TENG device is utilized to charge capacitors and power light-emitting diodes by scavenging the externally applied mechanical energy. This outstanding electrical performance makes b-PEN a promising tribopositive material.