An earlier structural model for binary silicate melts and glasses is extended to MF–BeF 2 (M=Li, K) systems. The evaluation of the thermodynamic properties as well as the phase diagrams for the binary LiF–BeF 2 system and the integral enthalpy of mixing of the KF–BeF 2 system are carried out with this model. This thermodynamic model is based on the assumption that each alkali fluoride produces the depolymerization of BeF 2 network with a characteristic free energy change. A least squares optimization program permits all available thermodynamic and phase diagram data to be optimized simultaneously. In this manner, data for these binary systems have been analysed and represented with a small number of parameters. The model predicts the chain-length distribution of polymeric ions, even though these are not explicitly treated as structural units of the model. The calculated fluoride polyanion chain-length distribution for the LiF–BeF 2 system is in quantitative agreement with the predictions reported in the literature.