Based on cluster molecular orbital calculations, high-energy resolution (Delta E ~ 0.4 eV) Ti L2,3 electron energy loss near-edge structures of single-crystalline and glassy Ba2TiGe2O8 are interpreted. The finding that the Ti L2,3 near-edge structure of the Ba2TiGe2O8 single crystal possesses less pronounced peaks than the glass under identical experimental conditions can be attributed to distinct distortions of the titanium environment caused by the very strong one-dimensional structural modulation hosted by the Ba2TiGe2O8 crystal lattice. As lattice periodicity is absent in the glass, the titanium environment is more regular in the vitreous surroundings. Moreover, the modulation in crystalline Ba2TiGe2O8 is responsible for the virtually indiscernible O K near-edge structures of the glassy and crystalline samples. ?2004 Taylor & Francis Ltd.