Glasses were prepared in the pseudobinary system Li3BO3-Li4GeO4 by a rapid quenching technique in the composition range of 8-80 mol% Li4GeO4. The structure of the glasses was examined by Raman spectra, X-ray diffraction analysis and molecular dynamics simulation. The coordination number of germanium atoms with respect to oxygen atoms in the glasses Li3BO3-Li4GeO4 was shown to be higher than four by the X-ray diffraction analysis. The Raman spectra showed that not only monomer ions of BO33- and GeO44-, but also dimer B2O(5)(4-) ions and six-coordinated GeO68- ions were present in these glasses over the whole glass-forming region. The presence of these ions was also confirmed from molecular dynamics simulation.