Animportant feature in Li batteries is the formation of a solid electrolyte interphase (SEI) on the surface of the anode. This film can have a profound effect on the stability and the performance of the device. In this work, we have employed density functional theory combined with implicit solvation models to study the inner layer of SEI formation from the reduction of common organic carbonate electrolyte solvents (ethylene carbonate, propylene carbonate, dimethyl carbonate, and diethyl carbonate) on a Li metal anode surface. Their stability and electronic structure on the Li surface have been investigated. It is found that the CO producing route is energetically more favorable for ethylene and propylene carbonate decomposition. For the two linear solvents, dimethyl and diethyl carbonates, no significant differences are observed between the two considered reduction pathways. Bader charge analyses indicate that 2 e(-) reductions take place in the decomposition of all studied solvents. The density of states calculations demonstrate correlations between the degrees of hybridization between the oxygen of adsorbed solvents and the upper Li atoms on the surface with the trend of the solvent adsorption energies.