Food grade W₁/O/W₂ Pickering double emulsions was prepared by using cassava nanostarch and cassava acetylated starch as the particle emulsifier, which were loaded with curcumin and anthocyanin on the inner water phase and oil phase, respectively. The effects of different mass fraction of cassava acetylated starch on the micro-morphology, particle size, Zeta potential, encapsulation efficiency and storage stability of the double emulsions were investigated, and its controlled release properties during in vitro digestion was analyzed. The results showed that at 6% of cassava acetylated starch, the comprehensive properties of double emulsions were better than that of other samples. The droplet distribution of emulsions was relatively uniform, and exhibited a “three-phase two membrane” structure. Particle size was 3.65μm, Zeta potential was -14.50mV, the encapsulation efficiency of curcumin and anthocyanin reached 95.23% and 93.00%, respectively, and there was no layering phenomenon after 20d storage at 4℃, 25℃, or 40℃. After simulated digestion, the retention efficiency of curcumin and anthocyanin were 41.59% and 76.29%, respectively. Compared with free curcumin and anthocyanin, their bioaccessibility increased by about 4 times and 3 times, which indicated that cassava starch-based double emulsions effectively protected active substance against simulated digestive system, and improved its bioaccessibility. The research results aimed to provide theoretical reference for the construction of functional starch-based emulsion delivery system in food industry and the creation of novel food grade Pickering double emulsions.