The combination of all-atom molecular dynamics simulations with differential scanning calorimetry (DSC) has been exploited to investigate the influence of temperature and hydration on the water distribution and mobility in poly(diallyldimethylammonium) (PDADMA) and poly(sodium 4-styrenesulfonate) (PSS) complexes. The findings show that the vast majority of the water molecules hydrating the polyelectrolyte complexes (PECs) with 18-30 wt % hydration are effectively immobilized due to the strong interactions between the PE charge groups and water. Temperature and hydration were found to decrease similarly the fraction of strongly bound water. Additionally, at low hydration or at low temperatures, water motions become dominantly local vibrations and rotations instead of translational motion; translation dominance is recovered in a similar fashion by increase of both temperature and hydration. DSC experiments corroborate the simulation findings by showing that nonfreezing, bound water dominates in hydrated PECs at comparable hydrations. Our results raise attention to water as an equal variable to temperature in the design and engineering of stimuli-responsive polyelectrolyte materials and provide mechanistic explanation for the similarity.