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This article reports the microstructural stability and consequent phase decomposition including the appearance of topologically close-packed (TCP) phases at high temperature of recently discovered tungsten-free γ–γ′ alloys of base composition Co–10Al–5Mo–2Nb with or without the addition of Ni and Ti. On prolonged aging at 800 °C of the Co–10Al–5Mo–2Nb alloy, needle-shaped DO₁₉-ordered precipitates with stoichiometry of Co₃(Mo, Nb) start appearing in the microstructure. In addition, growth of cellular domains from the grain boundaries featuring a three-phase composite lamellar structure could be observed. These phases are fcc γ-Co with composition different from the original matrix, CoAl with B2 ordering and Co₃(Mo, Nb) with DO₁₉ ordering. All the phases exhibit well-defined crystallographic orientation relationships. The decomposition of the alloys depends on the solvus temperature of the γ …