The effects of the addition of mixed cations, i.e. Na+/Cs+, Ba2+/Cs+, and Ba2+/Zn2+, to the acid form sulfonated styrene copolymers on their dynamic mechanical properties and morphology were investigated. It was found that the matrix glass transition temperatures did not change with the ratio of the one cation to the other. As expected, however, the ratio of one cation to the other in the mixed cations affected cluster glass transition temperatures significantly. It was also found that the activation energies for the glass transitions for the matrix phase remained constant, while those for the cluster phase changed with the ratio of the two cations. In addition, the position of the SAXS peak was found to be affected by the type of cations. From the results obtained above, the decrease in the cluster Tg with increasing the amount of cesium and zinc cations in Na/Cs, Ba/ Cs, and Ba/Zn mixtures, were explained on the basis of the considerations of the size, charge, and type of cations, which alter the degree of clustering as well as ion-hopping mechanism.