Lithium cation solvation structures [Li(S)_n=1–4]⁺ with ligands of cyclic or noncyclic carbamate-modified disiloxanes are optimized at B3LYP level of theory and compared to their corresponding simplified carbamates and to the organic carbonates ethylene carbonate (EC) and dimethyl carbonate (DMC). The electrostatic potentials (ESP) of these investigated carbonyl-containing solvents are mapped on the electron density surface. The maximum ESP is located at the CO-oxygen, whereas the disiloxane functionality represents an unpolar residue. Natural Bond Orbitals (NBO) analysis reveals strong n(N) → π(CO) donor–acceptor interactions in carbamates which outrun dipolar properties. As a result, higher total binding energies (ΔE_B) for solvation of Li⁺ in carbamates (−148 kcal mol⁻¹) are found than for carbonates (−137 kcal mol⁻¹). Furthermore, the disiloxane moiety with its Si–O bond is stabilized by n(O) → σ*(Si–C) hyperconjugation that provides additional electron density to a nearby SiCH₃ methyl group thus supporting an additional SiCH₂–H⋯Li⁺ coordination. The formation of all investigated solvation structures is exothermic. Owing to steric hindrance of noncyclic carbonyl-containing ligands and the bulky disiloxane functionality, the solvation structure [Li(S)₃]⁺ is the preferred structure according to Gibbs free energy ΔG_B results.