Conductance study of ion-pairing of dibenzo-24-crown-8 complexes with a series of sodium monoalkyl benzeneazophosphonates in acetonitrile has been described. The values of the ion-pair dissociation constants, K-D, and the limiting conductances, Lambda(0), of the complexes are reported. The results obtained are compared and discussed relative to the corresponding complexes of the 18-membered crown ether.