The synthesis and application of compounds with Cr–Cr and V–V d–d quintuple bonds (σ, 2π, 2δ) have led to new thinking about whether d–d multiple bonds also exist between early transition metals such as Sc–Sc and Ti–Ti. In this study, by extensive unbiased global search at the density functional theory level, the low-energy structures of 26e and 30e TM₂Li_n clusters were obtained. Based on the super valence bond (SVB) theory, the prolate double-core structure of TM₂Li_n clusters was regarded as a superatomic molecule, of which each half was regarded as an open-shell superatom, and the electronic shell-closure was realized by forming multiple bonds between superatoms. Then, the quintuple super bonds (2δ, 2π, σ) of the Li₁₈Ti₂, Li₂₀Sc₂, [Li₁₇V₂]⁺, [Li₁₇Ti₂]⁻ clusters and the triple super bonds (2π, σ) of the Li₂₄Sc₂ and Li₂₄Y₂ clusters were confirmed via chemical-bonding analysis. This way of forming multiple bonds between early transition metals through superatomic bonding has promoted the experimental synthesis and application of early transition metal multiple bond compounds.