Compositionally graded (Pb, Ca)TiO3 thin films were prepared on platinum-coated silicon substrates by a monoethanolamine-modified sol–gel technique. The crystalline orientation and surface morphology of the graded films were related to the deposition sequence of the film layer. The dielectric constants, for up-graded and down-graded films annealed at 600 °C for 60 min were found to be 504 and 399, respectively. Both were larger than those reported for conventional (Pb, Ca)TiO3 thin films. The compositionally graded films had large polarization offsets in hysteresis loops when driven by an alternating electric field. The magnitude of polarization offsets displayed a power-law dependence on the electric field, and the direction of the offsets depended on the direction of the composition gradient with respect to the substrate. The offset, 120 μC/cm2 at 300 kV/cm driving electric field, was obtained. These results showed that compositionally graded (Pb, Ca)TiO3 thin films had enhanced dielectric properties and abnormal ferroelectric properties which can be used in various microelectronic devices. © 2000 American Institute of Physics.