Current core–shell hybrids used in diverse energy-related applications possess limited dispersibility and film uniformity that govern their overall performances. Herein, we showcase superdispersible core–shell hybrids (P2VP@BaTiO3) composed of a poly(2-vinylpyridine) (P2VP) (5–20 wt %) and a barium titanate oxide (BaTiO3), maximizing dielectric constants by forming the high-quality uniform films. The P2VP@BaTiO3-based triboelectric nanogenerators (TENGs), especially the 10 wt % P2VP (P2VP10@BaTiO3)-based one, deliver significantly enhanced output performances compared to physically mixed P2VP/BaTiO3 counterparts. The P2VP10@BaTiO3-based double-layer TENG exhibits not only an excellent transferred charge density of 281.7 μC m–2 with a power density of 27.2 W m–2 but also extraordinary device stability (∼100% sustainability of the maximum output voltage for 54,000 cycles and ∼68.7% voltage retention even at 99% humidity). Notably, introducing the MoS2/SiO2/Ni-mesh layer into this double-layer TENG enables ultrahigh charge density of up to 1228 μC m–2, which is the top value reported for the TENGs so far. Furthermore, we also demonstrate a near-field communication-based sensing system for monitoring CO2 gas using our developed self-powered generator with enhanced output performance and robustness.