Electrostatic complexes based on chitosan, lecithin, and sodium tripolyphosphate were produced and evaluated with respect to their encapsulation capacity and cytotoxicity. Physical chemical properties were determined by zeta potential values and size distributions. For encapsulation assays, the emulsification method was followed, and Citrus senensis peel oil was utilized as volatile compound model. Morphology of complexes with oil incorporated was observed by scanning electron microscopy. The cytotoxicity of complexes was related to cell viability of zebrafish hepatocytes. The complexes produced presented positive Zeta potential values and size distributions dependent on the mass ratio between compounds. Higher concentrations of sodium tripolyphosphate promote significant changes (p < 0.05) in zeta values, which did not occur at smaller concentrations of the crosslinking agent. These complexes were able to encapsulate Citrus sinensis peel oil, with encapsulation efficiency higher than 50%. Cytotoxicity profiles showed that in a range of concentrations (0.1–100 μg/mL) studied, they did not promote cellular damage in zebrafish liver cells, being potential materials for food and pharmaceutical applications.