A new method to fabricate an Fe–PZT core–shell wire arrays developed in three steps is reported in this paper. This involves the electrochemical growth of an iron wire array by template method, deposition by spin coating of the PZT precursor prepared by sol–gel technique on the iron wires surface and annealing treatment to obtain Fe–PZT core–shell structures. The structure of the Fe–PZT core–shell wire array was characterized by scanning electron microscopy (SEM) and Raman scattering. Raman lines situated at 372 and 575 cm−1 indicate the formation of the FeO particles on the Fe wires surface as a result of the use of an aqueous solution for electrochemical synthesis. An upshift of Raman lines of Fe decorated with FeO wires was observed after formation of Fe–PZT core–shell structure. The annealing treatment of this structure involves a partial transformation of the FeO into Fe2O3 particles both with structure rhombohedral and cubic that were evidenced by Raman lines peaked at 243 and 497 cm−1, respectively.