Synthetic saponite (Sap) easily delaminates in water to form a transparent sol and hydrogel with excellent rheological performance and is thus widely used in paints, cosmetics, and nanomaterials. The thixotropic property of Sap hydrogels is heavily dependent on the nature of Sap and the external electrolyte and polyelectrolyte; yet, details on the relationship between rheological behaviors of saponite hydrogels and Sap composition and polyelectrolyte remain unclear. In this work, thixotropic rheological behaviors of a series of synthetic Sap hydrogels, with and without added sodium polyacrylate polyelectrolyte (NaPA), were investigated. The Sap samples, with a Si/Al molar ratio from 5 to 25, were successfully synthesized using hydrothermal methods and characterized by powder X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy. The rheological performances of aqueous Sap dispersions and particle sizes and zeta-potentials of Sap were measured. The results showed that the crystallinity of the Sap increased with an increasing Si/Al molar ratio. All Sap samples, with the exception of the Sap with a Si/Al molar ratio of 5, dispersed well in water (3 wt %) to form hydrogels. The rheological behaviors of the hydrogels were related to the chemical composition and the layer charge of the Sap. The Sap with a Si/Al molar ratio of 25 had higher viscosity due to improved delamination. The addition of the NaPA, an anionic polyelectrolyte, into the hydrogels decreased the viscosity and altered the thixotropic properties such that the hydrogel becomes a sol. The addition of NaPA facilitated the dispersion and delamination of Sap, because under the electric field of negatively charged Sap particles in the hydrogel, the anionic NaPA was instantaneously polarized and thereby entered the hydration layer of the Sap particles.