A composite structure with an highly flexible polymer substrate and a thin film of lead zirconate titanate, Pb(Zr,Ti)O3 (PZT), is realized using an all‐chemical process. The fabrication of the structure comprises three steps: first, PZT is deposited on an aluminum thin foil, then the PZT thin film is bonded to a polymer, and, finally, aluminum foil is removed by selective chemical etching. Structural characterization techniques are used to ensure the quality of the PZT/polymer composite structure. Electrical measurements are also performed to confirm the ferroelectric characteristics of the composite. Finally, energy harvesting measurements are realized with interdigitated electrodes structure. A maximal energy density of 20 μJ cm−2 is obtained with manual mechanical excitation and an output voltage up to 35 V under free oscillations conditions in bending mode. This demonstrates that the recently developed PZT/polymer thin films are very promising for low‐frequency vibrating energy‐harvesting applications.