•Ionically (Na+, Ca2+, K+) structured κ-carrageenan o/w emulsions were produced.•Cation type and amount impacted β-carotene chemical stability and bioaccessibility.•Ca2+ presence and high ionic strength reduced chemical stability of β-carotene.•Na+ and K+ o/g emulsions had higher β-carotene in vitro bioaccessibility.•Ca2+ presence influenced both colloidal and physical aspects of digesta. In the present paper, ionotropically structured κ-carrageenan based oil-in-gel (o/g) emulsions were tested as potential carrier systems for the delivery of β-carotene. In situ ionic gelation was induced by Na+, K+ or Ca2+ added at the level of 0.2–0.6% (w/w). All o/g emulsions exerted a true gel like behaviour with storage modulus (G′) being reduced according to the order: K+>Ca2+>Na+. Ionic gelation induced a moderate increase in the microscopically assessed lipid droplets radii. O/g emulsions containing monovalent ions exerted the highest β-carotene retention throughout isothermal storage particularly at high (37 and 55°C) temperatures. Notwithstanding, increasing ionic strength resulted in acceleration of β-carotene degradation rates for all cation species. β-Carotene bioaccessibility was significantly lower in Ca2+o/g emulsions due to the formation of complexes between the biopolymer matrix containing β-carotene and bile salts. A good correlation between β-carotene bioaccessibility, physical and colloidal aspects of the micellar digesta fractions was observed.