Exploring single-atom (SA) catalysts in hybrid urea-assisted water electrolysis offers a viable alternative to both Hydrogen (H2) generation and polluted water treatment. However, the unfavorable electronic stabilization, low SA content, intrinsically slow kinetics, and imbalanced adsorption-desorption steps are the bottleneck for its scale-up implementation. Herein, a rare-earth Terbium single atom (TbSA) is topologically stabilized on defect-rich Co3O4 (TbSA@d-Co3O4) by Tb─O co-ordination for urea oxidation reaction (UOR) and H2 evolution reaction (HER). Benefitting from the strong TbSA interaction with the d-Co3O4, the TbSA@d-Co3O4 achieves a 10 mA cm−2 current density at 1.27 V and −35 mV for UOR and HER, respectively. Remarkably, when TbSA@d-Co3O4 is applied as a bi-functional catalyst in a two-electrode system, it merely requires 1.22 V to acquire 10 mA cm−2 with excellent operational stability for 100 h. The hybrid electrolyzer can be successfully empowered by the triboelectric nanogenerator, AA battery, and solar panel with a nominal potential of 1.5 V. The mechanistic investigation predicts “TbSA” insertion in d-Co3O4 lowered the potential determining step, attributed to balanced reaction energetics for adsorption-desorption of intermediates and favorable charge transfer characteristics for UOR. This work offers a new paradigm to explore the catalytic properties of rare-earth “f-block” elements to create advanced electrocatalysts via structural modulation.