Ferroelectric PbTiO3thin films have been epitaxially grown on (100) NaCl cleavage surface by MOCVD using tetraethyllead and titanium isopropoxide as precursors. The microstructures and epitaxial characteristics of as-grown thin films were investigated by means of transmission electron microscopy. TEM studies have shown that the epitaxial thin film was highly (001) oriented and even near single-crystal epitaxy if without a small volume of 45° rotated grains, the average grain size is around 1000 A. Lowangle grain boundary formed universally when islands coalesced during the early stage of epitaxial growth. A possible growth mechanism has been given to explain this epitaxial phenomenon by consideration of two-dimensional coincidence superlattice. 90° ferroelectric domains were also observed both in the large matrix grains and small 45° rotated grains.