Reductive decomposition mechanisms for ethylene carbonate (EC) molecule in electrolyte solutions for lithium-ion batteries are comprehensively investigated using density functional theory. In gas phase the reduction of EC is thermodynamically forbidden, whereas in bulk solvent it is likely to undergo one-as well as two-electron reduction processes. The presence of Li cation considerably stabilizes the EC reduction intermediates. The adiabatic electron affinities of the supermolecule Li+(EC)(n) (n = 1-4) successively decrease with the number of EC molecules, independently of EC or Li+ being reduced. Regarding the reductive decomposition mechanism, Li+(EC), is initially reduced to an ion-pair intermediate that will undergo homolytic C-O bond cleavage via an approximately 11.0 kcal/mol barrier, bringing up a radical anion coordinated with Li+. Among the possible termination pathways of the radical anion, thermodynamically the most favorable is the formation of lithium butylene dicarbonate. (CH2CH2OCO2Li)(2), followed by the formation of one O-Li bond compound containing an ester group, LiO(CH2)(2)CO2(CH2)(2)OCO2Li, then two very competitive reactions of the further reduction of the radical anion and the formation of lithium ethylene dicarbonate, (CH2OCO2Li)(2), and the least favorable is the formation of a C-Li bond compound (Li carbides), Li(CH2)(2)OCO2Li. The products show a weak EC concentration dependence as has also been revealed for the reactions of LiCO3- with Li+(EC)(n); that is, the formation of Li2CO3 is slightly more favorable at low EC concentrations. whereas (CH2OCO2Li)(2) is favored at high EC concentrations. On the basis of the results presented here, in line with some experimental findings. we find that a two-electron reduction process indeed takes place by a stepwise path. Regarding the composition of the surface films resulting from solvent reduction, for which experiments usually indicate that (CH2OCO2Li)(2) is a dominant component, we conclude that they comprise two leading lithium alkyl bicarbonates, (CH2CH2OCO2Li)(2) and (CH2OCO2Li)(2), together with LiO(CH2)(2)CO2(CH2)(2)OCO2Li. Li(CH2)(2)OCO2Li and Li2CO3.