High-oleic palm oil is a food-grade oil with very attractive properties, as it is characterised by having an oleic acid concentration above 50% and a high content of vitamin E and provitamin A. This study investigated the effect of different combinations of two wall materials (whey protein (WP) and Capsul®, a commercial octenyl succinic anhydride modified starch (OSA-MS)) on the concentration of provitamin A, vitamin E and oleic acid, and the physical properties of high oleic palm oil emulsions encapsulated by Refractance Window drying technology. Wall material had a significant effect on vitamin E, carotenoid and oleic acid yield, being highest at an OSA-MS : WP concentration ratio of 1 : 3. Optimal results (minimum moisture content, water activity and hygroscopicity, and maximum encapsulation efficiency and phytonutrient yield) were achieved at an OSA-MS concentration of 8.13% and WP concentration of 91.87% and flakes were obtained as a novel solid structure to protect oil's phytonutrients. Interactions beyond the physical mixture between wall materials were observed in the polysaccharide region.