Lauric arginate (LAE) is a food-grade cationic surfactant that is a highly potent antimicrobial active against a wide range of food pathogens and spoilage organisms. In compositionally complex environments, the antimicrobial activity of cationic LAE is likely to be impacted by its interactions with other charged components. The purpose of this study was to characterize the interactions between cationic LAE and various food grade biopolymers with different charge characteristics: anionic (pectin, alginate, carrageenan, xanthan), neutral (dextran), and cationic (chitosan). Isothermal titration calorimetry (ITC) and turbidity measurements were used to characterize surfactant-biopolymer interactions and the solubility of any aggregates formed. ITC and turbidity measurements suggested that no complex formation occurred between the cationic LAE and the cationic or neutral biopolymers, although the critical micelle concentration (cmc) of the surfactant was changed because of excluded volume effects. On the other hand, ITC measurements indicated a strong binding interaction between cationic LAE and anionic biopolymers. The amount of surfactant bound and the solubility of the aggregates formed depended strongly on biopolymer type. The results of this study have important implications for the application of LAE in compositionally complex systems.