Structure property function relationships provide valuable guidelines for a systematic development of functional materials. It is demonstrated how an augmented bond valence (BV) approach helps to establish such relationships in solid electrolytes. In principle it permits to identify mobile species, transport pathways and provides estimates for ion mobilities. In this work we discuss ion conduction pathways in glassy Lithium metasilicate as an illustrative example. The required representative local structure model is derived from Molecular Dynamics simulations, which provides the opportunity to compare the bond-valence-based predictions from a static structure model with a comprehensive analysis of a complete simulation trajectory. It is shown that understanding the bond valence mismatch as an effective Morse-type interaction opens up a way for systematically analyzing ion transport pathways and for a generally applicable method with improved reliability to predict ion transport characteristics in solid electrolytes from the structure model.