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Objective Cationic guar is an important polysaccharide used as a hair conditioning agent in personal care products. In this article, we report streaming potential data demonstrating its behaviour as it interacts electrostatically with hair. Several cationic guar variants with different molecular weights (MWs) and charge densities (CDs) were examined. Methods All experiments were carried out with a custom‐designed streaming potential instrument so that in situ, real‐time data were monitored during the treatment of a hair plug with aqueous solutions of cationic guar and subsequent treatment with anionic surfactants—sodium laureth sulfate (SLES) and cocamidopropyl betaine (CAPB)—commonly found in contemporary shampoo formulations. Results The MW of the cationic guar variants plays an integral role in determining the thickness of the adsorbed polymer layer on the hair surface while CD influences the zeta potential. Data were also generated for the treatment of hair with a cationic flexible polymer (polyquaternium‐28) and cationic conditioning surfactant (behentrimonium chloride) to provide a frame of reference. The deposition behaviour on hair of high MW cationic guar variants is distinct from these conventional molecules in terms of its electrokinetic properties. We also examined the electrokinetic behaviour of cationic guar on hair types from different racial backgrounds. While the cationic guar treatment yielded similar results for the different hair types, anionic surfactant treatment resulted in quicker sorption and desorption from African, European 65% grey, and Mulatto hair as compared to Chinese, European dark brown, and Indian hair. Conclusion We introduce an in situ technique for measuring the dynamic sorption/desorption of charged molecules on the surface of human hair. Evaluation of a series of cationic guar species revealed varying behaviour depending on the MW and CD of the polysaccharide. Our data also demonstrate differences in the desorption properties of typical shampoo surfactants for hair from diverse racial backgrounds.