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A highly stable, cobalt rich, template free Co–AlPO material (Co1.16Al2P4O20H11.68) was prepared by opening the structure of cobalt methylphosphonate (CoMeP) layered material under hydrothermal (HT) treatment in the presence of aluminium. CoMeP serves as the structure directing unit favoring the preferential formation of Al–O–P bonds, thus connecting the neighboring layers, which results in alternating Co–P and Al stacks. The new Co–AlPO material is monoclinic (S.G.: P21/n), and it is built of 12 membered ellipsoidal channels running along the crystallographic c-axis containing confined water molecules and another 6 membered hexagonal channels along the a-axis, where Co2+ cations are occasionally found. The formation of Al–O–P bonds was proved by FTIR, Raman spectroscopy, and single crystal X-ray diffraction.