Conventional transition-metal cathodes constrained by a limited 3d-2p orbital manifold suffer from an unfavorable electronic structure that impedes the electrochemical kinetics of Li-CO₂ batteries. Incorporating rare-earth 4f orbitals introduces strong spin-orbit coupling and a delocalized f-p-d cascade, fundamentally remolding interfacial electronic landscape. Herein, asymmetric Gd-O-Mn active sites are constructed via a 4f-2p-3d gradient orbital coupling strategy by doping gadolinium into Mn₃O₄ nanorods. This establishes a cascaded Gd 4f-O 2p-Mn 3d electronic conduit inducing directional charge redistribution and augmented electron density. The electropositive Gd dopant simultaneously elevates the O 2p band center and activates lattice oxygen redox chemistry, facilitating both the nucleophilic attack on CO₂ and the subsequent cleavage of carbonate bonds. Consequently, the Gd-Mn₃O₄ cathode delivers an exceptional full discharge capacity of 14,640 mAh g^-1, a remarkably low overpotential of 1.23 V, and extended cycling stability over 230 cycles. Comprehensive experimental and theoretical analyses reveal the f-p-d cascade coupling not only preserves the structural integrity of the MnO₆ framework but also optimizes the adsorption energetics of key intermediates *C₂O₄. This work elucidates the mechanistic role of gradient orbital hybridization in stabilizing manganese-based cathodes and offers a new paradigm for the rational design of advanced catalytic sites in Li-CO₂ batteries cathodes.