The microstructure of Pt-modified γ′-Ni₃Al + γ-Ni coating on CMSX-4 single-crystal superalloy has been investigated by transmission electron microscopy (TEM). Cross-sectional TEM analyses showed the presence of precipitates in the coating. This precipitate was identified as the hexagonal topologically close-packed (TCP) μ phase with lattice parameters a = 0.473 nm and c = 2.565 nm. The energy-dispersive x-ray (EDX) spectrum of the μ phase suggested a refractory element rich compound comprising the elements Re, W, and Co. Twin domains parallel to (001) were found in the μ phase. The mechanisms of the μ phase and twinning formation were discussed.