Smooth a-axis oriented ZnO thin films are grown on (001) MgO substrates by pulsed laser deposition assisted by a very directional radio frequency oxygen plasma. The structure of the film is examined by X-ray diffraction, electron diffraction and high resolution electron microscopy. The film grows with vertical columns and is highly textured. Two preferential orientation relations between the ZnO film and the MgO substrate are observed: (101¯0) ZnO ||(002) MgO ; [0002] ZnO ||[200] MgO and (101¯0) ZnO || (002) MgO ; [1¯21¯0] ZnO || [200] MgO . The film/substrate interface is flat and strained because of the rather large lattice mismatch between the (101¯0) plane of ZnO and the (002) plane of MgO.