We have studied the rheological property evolution and hydration behavior of pure white portland cement (Type 1) pastes and concentrated cement-polyelectrolyte suspensions. Polyelectrolyte species have a marked effect on the initial stability, elastic property evolution (G'(t)), and hydration behavior of this cement system. Pure cement pastes exhibited an initial G' value of similar to10(4) Pa and fully reversible G'(t) behavior until the onset of the acceleratory period (t similar to 2 h), where the pastes stiffened irreversibly. In contrast, cement-polyelectrolyte suspensions exhibited initial G' values of similar to 1 Pa and G'(t) behavior comprised of both reversible and irreversible features. Their initial G' values, measured after disrupting the particle network under high shear conditions, grew exponentially with hydration time, where G(i)' = G(i,0)' exp(t/tau(c)) and tau(c) corresponds to the characteristic hydration time determined from calorimetry measurements. Our observations of these cement-polyelectrolyte systems suggest that hydration phenomena impact interparticle forces during early stage hydration and, ultimately, lead to initial setting through the formation of solid bridges at the contact points between particles within the gelled network.