The need to operate proton exchange membrane fuel cells under hot and dry conditions has driven the synthesis and testing of sulfonated poly(phenylene) sulfone (sPSO(2)) ionomers. The primary hydration and energetics associated with the transfer of protons in oligomeric fragments of two sPSO(2) ionomers were evaluated through first-principles electronic structures calculations. Our results indicate that the interaction between neighboring sulfonic acid groups affect both the conformation and stability of the fragments. The number of water molecules required to affect the transfer of a proton in the first hydration shell was observed to be a function of the hydrogen bonding in proximity of the sulfonic acid groups: three H2O for the meta- and four H2O for the ortho-conformations. Calculations of the rotational energy surfaces indicate that the aromatic backbones of sPSO(2) are much stiffer than the polytetrafluoroethylene (PTFE) backbones in perfluorosulfonic acid (PFSA) ionomers: the largest energy penalty for rotating phenylene rings (i.e., 15.5 kcal/mol for ortho-ortho-sPSO(2)) is nearly twice that computed for the rotation of a CF2 unit in a PTFE backbone. The energetics for the transfer of various protons in proximity to one or two sulfonate groups (-SO3-) was also determined. The computed energy barrier for proton transfer when only one sulfonic acid group is present is approximately 1.9 kcal/mol, which is 2.1 kcal/mol lower than similar calculations for PFSA systems. When two sulfonic acid groups are bridged by water molecules, a symmetric bidirectional transfer occurs, which gives a substantially small energy barrier of only 0.7 kcal/mol.