The liquid junction potential at a number of dissimilar solvent junctions has been determined within the framework of the tetraphenylarsonium tetraphenylborate extrathermodynamic assumption. The junctions investigated were H2O/solvent S, MeCN/solvent S and propylene carbonate (pcar)/solvent S. The liquid junction potentials obtained have primarily been related to solvent-solvent interactions at the junction, being, for water, lowest for an alcohol /H2O junction (10 mV) and the greatest for a dipolar aprotic/H20 junction (100-200 mV).