Supramolecular ionic networks combine singular properties such as self-healing behaviour and ionic conductivity. In this work we present an insight into the ionic conductivity and molecular dynamic behaviour of an amorphous and semicrystalline supramolecular ionic networks (iNets) that were synthesised by self-assembly of difunctional imidazolium dicationic molecules coupled with (trifluoromethane-sulfonyl) imide dianionic molecules. Relatively low ionic conductivity values were obtained for the semicrystalline iNet below its melting point (T-m = 101 degrees C) in comparison with the amorphous iNet for which the conductivity significantly increased (similar to 3 orders of magnitude) above 100 degrees C. Upon LiTFSI doping, the semicrystalline iNet reached conductivity values similar to 10(-3) S cm(-1) due to enhanced mobility of the network which was supported by solid-state static NMR. Furthermore, the overlapping of F-19 and Li-7 resonance lines from both the semicrystalline network and the LiTFSI suggests fast molecular motions. (C) 2015 Elsevier Ltd. All rights reserved.