The development of general strategies for the electronic tuning of a catalyst’s active site is an ongoing challenge in heterogeneous catalysis. To this end, herein, we describe the application of Li-ion battery cathode and anode materials as redox non-innocent catalyst supports that can be continuously modulated as a function of lithium intercalation. A zero-valent nickel complex was oxidatively grafted onto the surface of lithium manganese oxide (LixMn2O4) to yield isolated Ni2+ occupying the vacant interstitial octahedral site in the Li diffusion channel on the surface and subsurface of the spinel structure (Ni/LixMn2O4). The activity of Ni/LixMn2O4 for olefin hydrogenation, as a representative probe reaction, was found to increase monotonically as a function of support reductive lithiation. Simulation of Ni/LixMn2O4 reveals the dramatic impact of surface redox states on the viability of the homolytic oxidative addition mechanism for H2 activation. Catalyst control through support lithiation was extended to an organotantalum complex on LixTiO2, demonstrating the generality of this phenomenon.