There is considerable interest in developing delivery systems to encapsulate and protect chemically labile lipophilic food components, such as omega-3 rich oils. In this study, multilayer emulsion-based delivery systems were prepared consisting of omega-3 rich oil droplets coated by either caseinate (Cas) or lactoferrin–caseinate (LF–Cas). Surface deposition of LF onto Cas-coated oil droplets was confirmed by ζ-potential measurements. Emulsions containing lactoferrin and caseinate had better physical stability to pH changes and salt addition (pH 3–7, 0–50 mM CaCl2 at pH 7) than those containing only caseinate (pH 5–7, 0–2 mM CaCl2 at pH 7). The addition of LF also retarded the formation of lipid oxidation markers (hydroperoxides and thiobarbituric acid reactive substances) in the emulsions. The ability of LF to enhance both the physical and chemical stability of protein-stabilised emulsions is useful for the fabrication of delivery systems designed for utilisation within the drug and food industries.