For (Li2S)(x)(P2S5)(100-x) glasses and Li7P3S11 glass-ceramic, which are well-known lithium superionic conductors, the conduction pathways of lithium ions were predicted and visualized by combining reverse Monte Carlo (RMC) modeling and the bond valence sum (BVS) method using synchrotron X-ray and time-of-flight neutron diffraction data. The conduction pathways of the lithium ions could be classified into two types: lithium 'stable' and 'metastable' regions. In addition, it was found that a significant relationship exists between the topology of the conduction pathways of the lithium ions and the activation energy of the electrical conduction. (C) 2013 Elsevier B. V. All rights reserved.