In total, reaction between the multilayer BMP-TFSI film on graphite (0001) and Li during postdeposition of Li (3.6 ML) at room temperatures results already in significant decomposition of adsorbed BMP+Li and TFSI+Li species into volatile, C-and F-containing species, into molecular fragments and to some extent also already into more stable binary compound species. The molecular fragments exhibit BEs, which for most of their elements are either identical or rather close (OTFSI,dec-1, STFSI,dec-1, blue-yellow) in BE and hence in local environment to the coadsorbed BMP-TFSI and Li (FTFSI+Li, OTFSI+Li, STFSI+Li, CTFSI+Li, cyan) species. Only in the BMPrelated N1s peak they can be clearly distinguished (NBMP, red, NBMP,dec-1, green), indicating that this initial decomposition affects mainly the local environment of the N atoms in the adsorbed BMP species. In this respect, there is little difference to the decomposition behavior of BMP observed for the monolayer film, except that in the monolayer case this requires annealing, while for reaction with bulk BMP-TFSI this occurs largely already during Li post-deposition at RT. Further annealing to 450 K and 500 K causes stepwise decomposition of these molecular reaction intermediates into binary Li compounds or closely related species. Upon annealing to 650 K, also LiF-and LiCN-like adsorbed species (reactively) desorb completely, while O-and Scontaining compounds are still present on the surface. Also these trends are very close to the decomposition behavior observed for the monolayer film, indicating that the interaction of the adsorbed species with the graphite (0001) surface has little effect on their decomposition behavior. Also, there seems to be little difference in the interaction with an impinging Li 0 species, as encountered for the multilayer film, or with a coadsorbed Li + in the case of the monolayer film. Hence, the different initial states in these two cases seem to have little effect on the reactive decomposition behavior of BMP-TFSI, and the same is true also for the interaction of BMP-TFSI and its reaction products with the graphite (0001) substrate.