We demonstrate that K-shell photoelectron spectroscopy is sensitive to binding motifs of cationic cores with excess electrons in solvated metals. Hereby, the satellites in core-level spectra and not the main line provide the important insight into ion-pairing effects. We found that contact ion-pairs in Li-(NH3)(1-3) and a solvent-separated ion-pair in Li-(NH3)(4) result in remarkably different Li 1s spectra. The former spectra have numerous intense satellites of a charge-transfer character while that of Li-(NH3)4 contains only one strong satellite describing excitation of a solvated electron. We also explored K-shell photodetachment of the bare Li- and found that three-electron processes are essential here. (C) 2015 Elsevier B.V. All rights reserved.