We report on the growth of epitaxial La2/3Sr1/3MnO3 thin films on buffered Si(001) substrates. We show that a suitable choice of the buffer heterostructure allows one to obtain epitaxial (00h), (0hh), and (hhh) manganite thin films. The magnetotransport properties are investigated and we have found that the low-field magnetoresistance is directly related to the width of the normal-to-plane rocking curves, irrespective of the film orientation. The magnetic anisotropy of these films has also been determined.