Lead zircon titanate (PZT) composite films were advantageously prepared by a novel hybrid method of sol-gel and electrohydrodynamic jet (E-jet) printing. PZT thin films with thicknesses of 362 nm, 725 nm and 1092 nm were prepared on Ti/Pt bottom electrode via Sol-gel method, and then the PZT thick films were printed on the base of the PZT thin films via E-jet printing to form PZT composite films. The physical structure and electrical properties of the PZT composite films were characterized. The experimental results showed that, compared with PZT thick films prepared via single E-jet printing method, PZT composite films had fewer micro-pore defects. Moreover, the better bonding with upper and lower electrodes and higher preferred orientation of crystals were examined. The piezoelectric properties, dielectric properties and leakage currents of the PZT composite films were obviously improved. The maximum piezoelectric constant of the PZT composite film with a thickness of 725 nm was 69.4 pC/N, the maximum relative dielectric constant was 827 and the leakage current was reduced to 1.5 × 10−6A at a test voltage of 200V. This hybrid method can be widely useful to print PZT composite films for the application of micro-nano devices.