The microsolvation of Li+ in water is investigated. The ionization and double-ionization spectra of the series of (H2O)nLi+ (n = 1−5) clusters are calculated ab initio by Green's function methods and discussed in detail. The impact of the solvation of the lithium cation with an increasing number of water molecules on the spectral characteristics is revealed. In the context of microsolvation, the discussion of the results for the (H2O)5Li+ cluster is particularly important because the second solvation shell is accessed. Ionization- and double-ionization spectra may be considered to be very useful for the study of microsolvation clusters.