High internal phase emulsions (HIPE) are distinguished from ordinary emulsions by higher oil-phase percentage and better storage stability. Recently, HIPE stabilized with protein-based particles has received more attention. However, organic precipitation, chemical cross-linking and thermal denaturation are often needed to stabilize emulsions with natural proteins, and there is an urgent need to reduce the pollution of organic reagents. HIPE loaded with β-carotene stabilized by phycocyanin was prepared under mild conditions. It demonstrated strong stability in terms of temperature and storage, as evidenced by its 94.17% retention rate and 81.06% bioavailability. This stability was ascribed to the efficient defense against heat and UV rays, which was probably associated with the oil-droplet environment and interfacial protection of phycocyanin. It is speculated that the possible main interaction site between phycocyaninand sorbitol exists near amino acids 110 to 120 of the B chain. The hydrogen bond and hydrophobic interaction between them make the phycocyanin fully adsorbed on the oil-water interface when sorbitol is stable, forming a strong oil-water structure, which increases the stability of the emulsion. The outstanding fluorescence characteristics provide a feasible alternative for fluorescent emulsions to distribute and trace active compounds in vitro. HIPE loaded with β-carotene might have potential as a 3D printing material for edible functional foods. © 2024 Society of Chemical Industry.