Kinetic and thermodynamic properties of the products of the intercalation of lithium in layered transition metal oxides and sulfides are strongly determined by lithium coordinative environment. Thus, the electrode potentials as well as the activation energies for lithium diffusion are higher in MoO3 than in MoS2. A similar effect is appreciated for the products of the co-intercalation of lithium and poly(ethylene oxide) into MoS2. The effect of lithium coordinative environment on these properties may be understood by analyzing a theoretical model considering host-guest back-donation charge transfer achieved by the local polarization of the lithium ligands in the interlaminar spaces