We studied the interactions between gum Arabic and select catecholic compounds like caffeic acid, chlorogenic acid and catechol. We observed that GA is capable of promoting the auto-oxidation of the above-mentioned compounds into darkly colored pigments without the addition of redox-sensitive cations. Gum Arabic appeared to be unique among polysaccharide-based materials as many other types of polysaccharides promote the oxidation of the above-mentioned compounds only in the presence of redox cations like Fe 2+ or Cu 2+. RP-HPLC and SEC chromatographic techniques were employed to monitor the reactions and to observe the formation of high molecular mass, pigmented materials from gum Arabic and all three catecholic compounds. FT-IR spectroscopic analysis revealed that, despite their darkly colored appearances, the gum Arabic/pigment materials synthesized contain mostly gum Arabic and very little pigment. As chlorogenic acid is an ester of caffeic acid, we studied the capacity of gum Arabic to promote ester hydrolysis using acetylsalicylic acid as the model compound. We observed that gum Arabic did promote the hydrolysis of acetylsalicylic acid into salicylic acid. However, in all our experiments involving the pigment formation between gum Arabic and chlorogenic acid, we did not observe any evidence that chlorogenic acid was hydrolyzed leading to the release of caffeic acid during these reactions. In addition, we observed that heat treatment of gum Arabic did not affect its pro-oxidizing capability, but it did negatively affect its capability to hydrolyze salicylic acid. Thus, these two types of chemical reactivity present in the gum Arabic material may be associated with different components of the gum Arabic material.