The reaction of dimethyl carbonate (DMC) and diethyl carbonate (DEC) with clean metallic lithium in ultrahigh vacuum was studied by the use of X-ray photoelectron spectroscopy with the temperature-programmed reaction methodology. Both molecules are of interest as solvents in ambient-temperature lithium batteries. The solvent molecules were condensed onto the surface of an evaporated lithium film at 120 K, and spectra were collected as the sample was warmed in ca. 25 to 30-K increments. The reaction of either DMC or DEC with. lithium was initiated at 180 K, a temperature much lower than their bulk melting temperatures, producing lithium methyl carbonate, methyllithium and lithium ethyl carbonate, and ethyllithium, respectively. At temperatures greater than 270-300 K, the lithium alkyl carbonates start to decompose with Li2O, elemental carbon, and alkyllithium as products on the surface. Both DMC and DEC are more reactive toward metallic Li than another carbonate solvent, propylene carbonate, which we have studied by the same methodology. Because methyl and ethyllithium are highly soluble in the parent solvent, electrodeposited Li is predicted to have poor stability in an electrolyte composed of either DMC or DEC.