Abstract Highly polar tribolayers are essential for magnifying the output performance of triboelectric nanogenerators (TENGs). This study investigates the synergetic effect of tetraethylene pentamine‐functionalized reduce graphene oxide (rGO‐TEPA) and barium strontium titanate (BST) pillars on tribopositive and tribonegative layers, respectively. The surface potentials of pristine polyurethane (PU) and Ecoflex (EC0) increases by 2.2 (from 203 to 439 V) and 2.1 (from−848 to −1813 V) times their initial values by embedding 5 wt.% of rGO‐TEPA and 10 wt.% of BST, respectively. The optimized 2 wt.% of rGO‐TEPA loaded PU/5wt.% of BST loaded EC‐TENG (PU2/EC5‐TENG) produce a maximum open circuit potential (V OC ) of 440 V, short circuit current (I SC ) of 11.2 µA, and surface charge (Q) of 87 nC when employing a 12.5 N load at a frequency of 5 Hz. The PU2/EC5‐TENG shows an output performance (V OC ) ≈2.7 times higher than PU/EC0‐TENG, revealing the capability of the rGO‐TEPA and BST pillars to enhance the performance of TENGs. The optimized PU2/EC5‐TENG shows a maximum power density of 0.58 Wm −2 at 70 MΩ and demonstrate real‐time applications such as lighting LEDs (100 no's) and low‐power LCD display (stopwatch). This demonstrates the applicability of the proposed PU2/EC5‐TENG in self‐powered low‐power electronics.