Epitaxial ZnO films have been grown on Si(111) substrates by employing a AlN buffer layer during a pulsed laser-deposition process. The epitaxial structure of AlN on Si(111) substrate provides a template for ZnO growth. The resultant films are evaluated by transmission electron microscopy, x-ray diffraction, and electrical measurements. The results of x-ray diffraction and electron microscopy on these films clearly show the epitaxial growth of ZnO films with an orientational relationship of ZnO||Aln||Si along the growth direction and ZnO[2 1
1 0]||AlN[2 1
1 0]||Si[0 1
1] along the in-plane direction. High electrical conductivity (103 S/m at 300 K) and a linear I-V characteristics make these epitaxial films ideal for microelectronic, optoelectronic, and transparent conducting oxide applications.