MCrAlY (M = Ni and/or Co) metallic coatings are essential for the protection of hot-end components against thermal and corrosion damage. Increasing the Al content is considered a feasible solution to improve the high-temperature performance of MCrAlY coatings. In this paper, the effects of high Al contents (12–20 wt.%) on the phase constituents and cast microstructures in MCrAlY alloys were studied by high-energy X-ray diffraction and electron microscopy techniques combined with phase equilibria calculations. High Al content improved the stability of β, σ, and α phases. Meanwhile, an evolution of the cast microstructure morphology from a dendrite structure to an equiaxed grain structure was observed. The thermal properties were analyzed, which were closely related to the phase constituents and solid-to-solid phase transitions at evaluated temperatures. This work is instructive for developing high-Al-content MCrAlY coatings for next-generation thermal barrier applications.