A 750 nm-thick PZT-PMN/PZT composite film was prepared by sequential multiple spin-coatings. First, a 375 nm-thick sol-gel Pb (Zr0.56Ti0.44)O3 (PZT) layer was prepared on a Ti/Pt/Ti bottom electrode and then a 375 nm-thick Pb (Zr0.56Ti0.44)0.80 (Mg1/3Nb2/3)0.20O3 (PZT-PMN) layer was prepared on the PZT layer. The structural, compositional and piezoelectric properties of the composite film were investigated by using X-ray diffraction, scanning electron microscopy, cross-sectional transmission electron microscopy and secondary ion mass spectrometry and by measuring the piezoelectric charge constant d31, the piezoelectric voltage constant g31 and the relative permittivity ∈. The composite film retains the tetragonal perovskite structure with columnar grains. The lattice of the PZT-PMN layer smoothly connects to that of the PZT layer without forming any interfacial structure. However, the atomic composition, mainly in Mg and Nb, differs between PZT-PMN and PZT layers. The composite film has a higher piezoelectric charge constant d31 as compared with the PZT-PMN and PZT single films. The value of d31 is independent of the sequence of the PZT-PMN and PZT layers.