Abstract In this work a gel was formed by complexation of two natural polyelectrolytes, chitosan and xanthan. Changes in the hydrogels rheological properties have been studied in terms of hydrogel concentration (7–10% w/w), chemical media used for the hydrogel dispersion, and ‘test lag time’; i.e., the time between hydrogel dispersion in the chemical media and the start of the rheological test (up to 390 min). The viscoelastic properties of this polysaccharide system were characterized by oscillatory shear measurements under small-deformation conditions and the results show that chitosan/xanthan hydrogels behave like weak gels. The shear modulus increased almost linearly with frequency in the range studied (0.1–65 s −1). The effects of hydrogel concentration and dispersion medium have been related to electrostatic equilibrium and by the presence of counter-ions modifying the internal structure of the hydrogel.