The Fe73.5Cu1Nb3Si13.5B9/PZT thick film composites with excellent magnetoelectric (ME) coupling effect were synthesized by electrostatic spray depositing. The ME coupling characteristics of Fe73.5Cu1Nb3Si13.5B9/PZT thick film composites were investigated. It is found that the appropriate thickness ratio between magnetostrictive layers and piezoelectric layers (tm/tp) will be favorable to raise the resonance ME field output performance. The resonance frequency of ME field coefficient can be tuned by controlling tm/tp. The optimum resonance ME field coefficient of Fe73.5Cu1Nb3Si13.5B9/PZT thick film composites achieves 259.2 V/cm Oe at mechanical resonance frequency at 11.5 kHz with the dc bias magnetic field is 60 Oe. Remarkably, the proposed composites exhibit a giant ME effect and a higher ME voltage coefficient than the previous Terfenol-D/PZT laminated composites. It indicates that the mentioned Fe73.5Cu1Nb3Si13.5B9/PZT thick film composites have great potential for the application of highly sensitive magnetic field sensing and vibration energy harvesting.