We report on the properties of ferroelectric Pb(Zr0.2Ti0.8)O3 (PZT) thin films grown epitaxially on (001) silicon and on the performance of such heterostructures for microfabricated piezoelectric energy harvesters. In the first part of the paper, we investigate the epitaxial stacks through transmission electron microscopy and piezoelectric force microscopy studies to characterize in detail their crystalline structure. In the second part of the paper, we present the electrical characteristics of piezoelectric cantilevers based on these epitaxial PZT films. The performance of such cantilevers as vibration energy transducers is compared with other piezoelectric harvesters and indicates the potential of the epitaxial approach in the field of energy harvesting devices.