A sol‐gel spin‐coating procedure was established to prepare La0.5Sr0.5CoO3/ PbZr0.56Ti0.44O3/La0.5Sr0.5CoO3multilayer structure on SrTiO3(100) and LaAlO3(100) substrates. The films were characterized by means of x‐ray diffraction, scanning electron microscopy, and electrical measurements. The results showed the advantages of the sol‐gel processing in compositional control as well as in oriented growth of films. A high remnant polarization was obtained in the films prepared with this procedure. ©1995 American Institute of Physics.