Solvation states of single solvent electrolyte systems of ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), ehylmethyl carbonate (EMC) and diethyl carbonate (DEC) with LiPF6 were characterized by C-13-NMR solvation shift and molecular orbital (MO) simulation. Dissociation constants and solvation constants were estimated by parameter fitting to solvation shift using a simple equilibrium model, The solvation shifts Delta delta were observed not only at a lower field but also at a higher field due to change of net charge Delta rho in solvent molecules by Li+ attachment. This particular feature of solvation shifts was demonstrated in the molecular orbital simulation as driven by the change of net charge using a 1:1 (Li+:solvent) solvation model.