We report on the role of ester bonds in the enhanced removal of hexavalent chromium from water using cotton fibers coated with chitosan. Adsorption capacities up to five times higher than those of the unmodified fibers were observed when the cotton fibers were exposed to an NaOH, followed by citric acid (0.97 M), and a chitosan solution (2%). We found that the use of NaOH favors the formation of ester bonds over amide bonds on the surface of the cotton fibers. This increase in the surface density of ester bonds generates an increase in the amount of exposed amino groups from the chitosan, hence increasing the removal capacity of the modified fibers. Experimental results also reveal that the adsorption is induced by the electrostatic attraction between the protonated amino groups on the surface and the negatively charged chromium ions in the water. Adsorption isotherms and kinetic studies indicated that the adsorption process fits the Langmuir and the Freundlich isotherm models as well as the pseudo-first and pseudo-second order kinetic models. These results can open a new avenue for the manufacturing of fibers with enhanced removal capacities for hexavalent chromium.