Electrospun nanofibers from copolymers composed of ferrocene side chains and PEO100‐PPO65‐PEO100 (F127) were fabricated in chloroform and N,N–dimethyl formamide solutions (V/V = 95:5) at room temperature. Ferrocene‐containing multiblock copolymers (PFcMAn‐F127‐PFcMAn) were synthesized through reversible addition‐fragmentation chain transfer polymerization using s‐1‐dodecyl‐s''‐ (α, α'‐dimethyl‐α''‐acetic acid) trithiocarbonate (DDMAT) modified F127 with 2‐ (methacryloyloxy) ethyl ferrocencarboxylate (FcMA). The structures of as‐obtained chemicals were characterized by FTIR, 1H NMR, and 13C NMR. Additionally, the block copolymers molecular weight and polydispersity were measured using gel permeation chromatography. The electrochemical responsiveness of the polymers was investigated using cyclic voltammetry as well as the thermal stabilities of polymers and precursors were tested through DSC and TGA. The morphologies of electrospun fibers were observed through field emission scanning electronic spectroscopy and a fibrous diameter of 300–1100 nm was obtained. The results indicated that the suitable molecular weight of ferrocene ‐containing polymer would be processed in nanofibrous.