SPEEK is known to possess high proton conductivity at high water content, being comparable with other popular membranes used in fuel cells, such as Nafion and sulfonated polyethersulfone (SPES). However, much less is known about its fundamental properties, including the status of proton dissociation and spectral features. In this work, the properties of two model molecules of SPEEK, M1 (20 atoms), M2 (50 atoms) and their hydrated systems, M1 + nH₂O and M2 + nH₂O (n = 1–9), have been investigated using static electronic structure calculations and the ab initio molecular dynamics (MD) method. Optimized structures for all of the systems and the trajectories of M1 + nH₂O (n = 3–6) at finite temperatures have been computed using density functional theory at the B3LYP level of theory. Proton dissociation has been discussed in detail, especially for n = 3 and n = 4. In addition, the infrared spectra of SPEEK and its hydrated systems have been studied using a combination of theory and experiment. The characteristic bands of SPEEK and the surrounding water clusters have been assigned with emphasis on their relationship with the degree of proton dissociation. We have found that the hydronium ion stretching modes, which appear in the 2000–3000 cm⁻¹ region in static electronic structure calculations, are not observed experimentally. This discrepancy is explained by the stationary structure and the temperature effect.