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The Al–Sm and Al–Ca phases thermal stability effect on mechanical properties of Mg–3Al–2Ca–2Sm alloy was studied. When the isothermal treatment temperature is 200°C and 300°C, the second phase formed in as-cast Mg–3Al–2Ca–2Sm alloy does not change significantly. The Al 2 Ca and Mg 2 Ca precipitated phases were precipitated during isothermal treatment. The alloy exhibits favourable tensile strength, elongation and fracture toughness. By increasing the isothermal treatment temperature to 400°C or even higher, the second phase began to decompose, except for the original particle Al 2 Sm phase. The acicular Al 11 Sm 3  phase breaks down into the particle Al 2 Sm phase. Furthermore, the fish-bone Al 2 Ca phase and lamellar (Mg, Al) 2 Ca phase decompose into particle Al 2 Ca phase. The mechanical properties and fracture toughness of the alloy decrease gradually.