The natural cationic polysaccharide chitosan was mixed with the nonionic surfactants sorbitan monolaurate, sorbitan monooleate, or sorbitan triooleate to produce a biopolymer-surfactant system with unique properties. The mixtures of chitosan and surfactant formed emulsion-like solutions and/or creams. The known properties of the components were considered (i.e., hydrophile-lipophile balance, molecular weight, structure, and density), and various physicochemical and theological properties of the mixtures were measured. Specifically, the critical micelle concentration of the sorbitan esters in a chitosan solution was measured using both surface tension and fluorescence-based methods. The concentration-dependent morphologies of the aggregates within the chitosan-surfactant solutions were evaluated by optical microscopy and dynamic light scattering. A schematic depicting the possible molecular arrangement of chitosan and surfactant within the various formulations was produced from consideration of the experimental findings. The degree of interaction between chitosan and the individual surfactants was assessed by FTIR analysis. The theological properties of the chitosan-surfactant emulsions were also investigated and found to be related to the observed morphologies. Overall, clear composition-property relationships were established for these chitosan-surfactant systems which have potential applications in the food and pharmaceutical industries.