Our augmented bond valence approach may be used to establish structure–property relationships in solid electrolytes, to identify the mobile species and to locate energetically favorable transport pathways for the mobile type of ions through the bond valence sum mismatch “landscape” created by the immobile substructure. Here ion transport pathways of crystalline and glassy Li+ ion conductors are analysed. Beyond the visualization of pathways the bond valence analysis also provides assessments of the relevant activation energies and thereby helps to clarify transport mechanisms and to identify promising novel ion conducting materials. The approach is particularly useful for the analysis of disordered systems such as ion conducting glasses, where particularly strong structure conductivity correlation has been identified.