This study examines the influence of interfacial composition on the freeze–thaw stability of oil-in-water emulsions. Three 5% w/w oil-in-water emulsions (5 mM phosphate buffer, pH 6.0) were prepared using the layer-by-layer electrostatic deposition method that had different interfacial compositions: (i) primary emulsion (β-Lg); secondary emulsion (β-Lg–ι-carrageenan); (iii) tertiary emulsion (β-Lg–ι-carrageenan–gelatin). The primary, secondary and tertiary emulsions were subjected to from one to three freeze–thaw cycles (−20 °C for 22 h, +40 °C for 2 h) in the absence or presence of sucrose (10% w/w), and then their stability was assessed by ζ-potential, particle size, microstructure and creaming stability measurements. In the absence of sucrose, the primary and secondary emulsions were highly unstable to droplet aggregation and creaming after three freeze–thaw cycles, whereas the tertiary emulsion was stable, which was attributed to the relatively thick biopolymer layer surrounding the oil droplets. In the presence of 10% w/w sucrose, all of the emulsions were much more stable, which can be attributed to the ability of sucrose to increase the amount of non-frozen aqueous phase in the emulsions. The interfacial engineering technology used in the study could therefore lead to the creation of food emulsions with improved stability to freezing and thawing.