Rheological structuring and tunability of surfactant solutions is a vital aspect of product formulation for pharmaceutical, cosmetic and consumer product applications. Sulfate-free anionic surfactants (amino acid-based or bio-based surfactants) do not tend to build adequate structure and exhibit slow response in the presence of zwitterionics and salts unlike their sulfate-based counterparts which are able to respond quickly to external stimuli (change in pH and electrolyte concentration) via the formation of worm-like micelles. We explored an alternate structuring approach to establishing stimuli responsiveness in a mixed sodium laurylglucosides hydroxypropyl sulfonate (SLHS)-based surfactant system, through engineered surfactant-polymer interactions. We report in this work that the interplay of hydrophobic and electrostatic interactions between the mixed system of SLHS and Cocamidopropyl Betaine (CAPB) with Carrageenan produces a synergistic increase from ∼103 to ∼106 mPa.s in viscosity of the overall system, giving rise to a structuring mechanism which is tunable and responsive to external stimuli- such as variation in pH or electrolyte levels. This finding may prove helpful to formulators in related fields for the development of sulfate-free formulations which impart a novel and differentiated consumer experience.