Microstructures in the thin film of La0.8Sr0.2MnO3 grown on (100) SrTiO3 by laser molecular beam epitaxy were characterized by transmission electron microscopy. Highly dense and dimensionally uniform nano-agglomerates were found embedded in thin film of La0.8Sr0.2MnO3. High-angle angular dark-field imaging, elemental mapping, and compositional analysis revealed that the nano-agglomerates are rich in manganese and poor in lanthanum. The ratio of Mn/La in the nano-agglomerates fluctuates. A salient feature of this compositional fluctuation within the nanoscale isthe formation of cubic MnO phase, which appears as the core of the nano-agglomerates.The La0.8Sr0.2MnO3 film is domain-oriented and two domains were identified on the basis of orthorhombic lattice. The orientation relationships between La0.8Sr0.2MnO3 domains and MnO were determined as LSMO,1//MnO and (100)LSMO,1//(110)MnO; LSMO,2//MnO and (010)LSMO,2//(100)MnO. The domain structuresand compositional inhomogeneities within nanoscale result in a textured microstructure, which is one of the most important parameters for tuning electronic properties in colossal magnetoresistance oxides.