Oxidative protection of mayonnaises with 16% fish oil was studied during cold storage (5 °C) after supplementation with different tocopherol systems: the ternary antioxidant system ascorbic acid, lecithin and tocopherol (A/L/T), and two commercial mixtures, an oil-soluble (Toco 70) preparation and a water-soluble (Grindox 1032) preparation. The physical structure of the fish-oil-enriched mayonnaise was manipulated by adding extra emulsifier (Panodan TR) with the purpose of investigating whether or not this affected the antioxidative activity of the tocopherol mixtures. A number of different analytical techniques HPLC (high-performance liquid chromatography, gas chromatography mass spectrometry (GC-MS), sensory analysis, confocal laser scanning microscopy and rheological measurements) were employed to elucidate the chemical, sensory, structural and rheological aspects of the oxidation process. Discriminant partial least squares regression was used to analyse the data obtained. The three tocopherol preparations not only affected the oxidative stability of the mayonnaises differently, they also influenced the rheological and structural properties of the mayonnaises in different ways. The rheological and structural properties of the mayonnaise were also affected by the addition of extra emulsifier, but this did not influence the formation of fishy and rancid off-flavours. Addition of the A/L/T system caused the immediate formation of distinct fishy and rancid off-flavours in the fresh mayonnaises. The volatile compounds trans-2-heptenal, 4-octen-3-one, 1-octen-3-ol, trans,cis2,4-heptadienal, trans,trans-2,A-heptadienal, trans-2-octenal, nonanal and trans,cis-2,6-nonadienal were thought to contribute to the fishy and rancid flavours. Addition of Toco 70 did not affect the sensory perception of mayonnaise nor the development of volatile off-flavour compounds as evaluated by GC-MS, but the peroxide values were slightly increased in mayonnaise containing Toco 70 as compared to the other mayonnaises. Mayonnaise with Grindox 1032 seemed to have fewer fishy and rancid off-flavours than mayonnaises without antioxidant. This flavour-protective effect of Grindox 1032 was correlated to an increase in the size of the droplet diameter of mayonnaises supplemented with Grindox 1032.