Vitamin E is an essential micronutrient for humans and animals due to its antioxidant and non-antioxidant biological activities. The α-tocopherol acetate form is often used in foods and other products due to its high biological activity and chemical stability. In this study, we examined the influence of carrier oil type on the bioaccessibility and molecular form of emulsified vitamin E using a simulated gastrointestinal model. Oil-in-water emulsions containing α-tocopherol acetate were prepared using quillaja saponin as a natural surfactant, and either long chain triacylglycerols (LCT) or medium chain triacylglycerols (MCT) as carrier oils. The rate and extent of lipid digestion was higher for MCT- than LCT-emulsions, which was attributed to differences in the water dispersibility of the free fatty acids formed during lipolysis. Conversely, the total bioaccessibility of vitamin E after digestion was higher for LCT- than MCT-emulsions, which was attributed to the greater solubilisation capacity of mixed micelles formed from long chain fatty acids. The conversion of α-tocopherol acetate to α-tocopherol after in vitro digestion was also considerably higher for LCT- than MCT-emulsions, which may impact the subsequent absorption of vitamin E. Overall, this research has important implications for the design and fabrication of effective emulsion-based delivery systems for increasing the bioavailability of vitamin E.