We report the epitaxial growth of (0 0 1), (0 1 1), and (1 1 1) oriented La2/3Sr1/3MnO3 (LSMO) thin films on Si(0 0 1) with multiple buffer layers by pulsed laser deposition. The crystal structure of the three heterostructures has been studied by X-ray diffraction analysis. Studies on the in-plane crystallographic relations revealed a different epitaxial nature of distinct orientations giving rise to a distinct degree of in-plane structural coherence. Cube, rectangle, and triangle on cube epitaxy is described in detail.