Calcium cobaltite thin films with a ratio Ca/Co=1 were grown on (101)-NdGaO3 substrate by the pulsed laser deposition technique. The structure of the deposited metastable phase is solved using a precession electron diffraction 3D dataset recorded from a cross-sectional sample. It is shown that an ordered oxygen-deficient Ca2Co2O5+d perovskite of the brownmillerite-type with lattice parameters a= 0.546nm, b=1.488nm and c=0.546nm (SG: Ibm2) has been stabilized using the substrate induced strain. The structure and microstructure of this metastable cobaltite is further discussed and compared to related bulk materials based on our transmission electron microscopy investigations
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