The ferroelectric properties of lead zirconate titanate (PZT) and lanthanum-doped lead zirconate titanate (PLZT) multilayer films formed by photochemical metal-organic deposition (PMOD) using photosensitive precursors have been characterized. The substitution of La for Pb was reported to induce improved ferroelectric properties, especially fatigue resistance, through the reduction of oxygen vacancies. The relation between La-substitution and the ferroelectric properties was investigated by characterization of the effect of the order of stacking four ferroelectric layers of PZT or PLZT in the multilayer films 4-PZT, PZT/2-PLZT/PZT, PLZT/2-PZT/PLZT, and 4-PLZT. The films with the PLZT layer at the top and bottom showed an improvement in the fatigue resistance. It was revealed that defect dipole such as O vacancy was reduced at the ferroelectric/Pt interface by doping with La. Also, the bottom layer, just on Pt substrate had a significant influence on the surface microstructure and growth orientation of ferroelectric film. (C) 2004 Elsevier B.V. All rights reserved.