Chitosan is a cationic biopolymer, which attracts more and more attention in recent years, due to its exceptional physical and chemical properties, expressive biocompatibility and possibilities of obtaining from renewable sources. Formed polymer/surfactant complexes affect changes in the rheological properties and the final result is the formation of coacervates. The purpose of this study was to investigate the rheological properties of aqueous solutions of cationic polyelectrolyte, chitosan and sodium lauryl ether sulfate (SLES), an anionic surfactant, widely used in the cosmetics industry. Using the Thermo Haake RS600 rheometer, changes in the rheological and elastic properties of chitosan and SLES mixtures have been identified, gained as a result of the interaction of the components. In all examined samples coefficient of thixotropy was increasing with increase SLES concentration and achieves a maximum value at the mass ratio chitosan:SLES 1:2, after which it reduces. The oscillatory measurements in mixtures, performed by amplitude sweep method at low oscillating frequency 1 Hz, show that the linear viscoelastic region increases with increasing SLES concentration up to the same chitosan:SLES mass ratio. By monitoring the changes in the rheological parameters of the mixtures over five days, it was observed that the viscosity, the coefficient of thixotropy and elasticity were increasing, indicating that changes in the system occur over a longer period of time. In that manner, obtained results indicate the possibility of using rheological methods for a more detailed description of the interaction in the chitosan/SLES mixtures, important for their application in cosmetics and pharmaceutical industries.