Lithium fluorophosphate (LFP) glasses doped with 1 mol% MoO3 were prepared and characterized by various experimental methods. Remarkable changes have been observed in the spectra with changes in preparation temperature, concentration and composition of the glasses. The glass transition temperatures were determined and the thermal stability tested. The structure and nature of bonding in the glasses have been discussed. The bonding orbital coefficients have been evaluated. © 2005 Elsevier B.V. All rights reserved.