In this article we report our findings on the electronic structure of the Li induced Ge(1 1 1)–3 × 1reconstruction as determined by angle-resolved ultraviolet photoelectron spectroscopy (ARUPS) and core-level spectroscopy using synchrotron radiation. The results are compared to the theoretical honeycomb-chain-channel (HCC) model for the 3 × 1reconstruction as calculated using density functional theory (DFT). ARUPS measurements were performed in both the and directions of the 1 × 1 surface Brillouin zone at photon energies of 17 and 21.2 eV. Three surface related states were observed in the direction. In the direction, at least two surface states were seen. The calculated band structure using the single-domain HCC model for Li/Ge(1 1 1)–3 × 1 was in good agreement with experiment, allowing for the determination of the origin of the experimentally observed surface states. In the Ge core-level spectra, two surface related components were identified, both at lower binding energy with respect to the Ge bulk peak. Our DFT calculations of the surface core-level shifts were found to be in fair agreement with the experimental results. Finally, in contrast to the Li/Si(1 1 1)–3 × 1 case, no double bond between Ge atoms in the top layer was found