With a high-resolution two-crystal vacuum spectrometer equipped with beryl crystals, the Ge L α emission and Ga L α emission spectra in fluorescence have been measured for Ge, GeO 2 , GaP, GaAs and Ga 2 O 3 . The measured L α emission spectra consist of a prominent peak L α 1,2 and its high-energy structure, and are slightly influenced by chemical bonding. The L α emission spectrum of Ge is compared with available multiplet calculations for Ge L α 1,2 satellites. The high-energy structure is primarily attributed to the satellites as a result of multiple ionizations.