X-ray photoelectron spectroscopy (XPS) was used to examine the reactivity of metallic Li toward gas-phase symmetric and asymmetric alkyl linear carbonates of the form ROCO2R' (R and R' = -CH3, -CH2CH3) at room temperature in ultrahigh vacuum (UHV). Comparison of the C (1s) and O (1s) XPS features obtained in virtually identical experiments involving methanol and ethanol allowed LiOCH3 and LiOCH2CH3 to be clearly identified as the major products of the reaction between Li and dimethyl (DMC) and diethyl (DEC) carbonates, respectively, and a mixture of the two alkoxides for ethylmethyl (EMC) carbonate. These findings are in agreement with UHV Fourier transform infrared studies of the same systems reported earlier in our laboratory. Also found in the XPS spectra for ROCO2R'/Li interfaces was an O (1s) peak at 529.6 eV attributed to Li oxide. In the case of DEC and EMC, evidence was obtained for the presence of an additional O (1s) feature at 534.76 eV attributed to Li ethyl carbonate. This behavior was unlike that found for DMC for which no signals due to Li methyl carbonate could be discerned. The conclusions emerging from this study further support the general mechanism for Li reactivity toward ROCO2R' suggested by Aurbach and co-workers.