In this work, Fe/Fe₃C–C₄N PON is synthesized through the anchoring of Fe/Fe₃C nanoparticles on the nitrogen-doped sites of pyrazine rings of two-dimensional fused aromatic porous organic networks (2D C₄N FA-PON). It significantly improves the tribo-charge generation for triboelectric nanogenerators (TENGs) and electric double-layer capacitance (EDLC) for supercapacitors. The Fe/Fe₃C–C₄N PON-based TENG can generate electric outputs of 14.5 µA and 380.9 V compared to 3.2 µA and 34.3 V for C₄N FA-PON, which is attributed to enhanced charge transport, interfacial polarization, and charge trapping. Furthermore, this structure achieves a capacitance of 290.4 F g⁻¹ in KOH and 406.7 F g⁻¹ in tetraethylammonium tetrafluoroborate (TEATFB) at a current density of 2.5 mA, compared to 72.1 and 152.2 F g⁻¹ for C₄N FA-PONs in the same electrolytes. The incorporation of Fe/Fe₃C provides a shift toward EDLC behavior and expands the potential window in KOH from 0.6 to 1.2 V and in TEATFB from 0.7 to 2 V. Moreover, density functional theory (DFT) supports that incorporation of Fe/Fe₃C into C₄N FA-PONs significantly enhances stability, hydrogen adsorption capability, and shows the filling of the bandgap region. These results highlight the advantage of anchoring pyrazine-based 2D FA-PONs as potential materials for advanced energy harvesting and storage systems.