Metallopolymers are emerging as a class of promising materials due to versatile properties and functionalities with a broad range of applications in high-performance devices. In this paper, a series of new helix coil helix poly(gamma-benzyl-L-glutamate)-b-poly(ethylene glycol)-b-poly(gamma-benzyl-L-glutamate) triblock copolymers selectively decorated with cyanoferrate complex (BEB-Fe) was successfully synthesized by combining ring-opening polymerization of gamma-benzyl-L-glutamate carboxyanhydride using a primary amine terminated poly(ethylene glycol) as macromolecular initiator with a post-functionalization procedure. The polymers were characterized using GPC, NMR, UV-vis, FT-IR, CD, XRD, DLS, TEM, DSC and CV. Microstructural and morphological analysis revealed that incorporation of a proper amount of ferrate complex (>= 19 wt%) in BEB led to disassembly of hexagonally packed structures of EBE. This afforded hybrid nanostructures with a size of approximately 18 nm. Glass transition temperature of BEB-Fe increased gradually with increasing ferrate fractions. BEB-Fe hybrid nanomaterials were electrochemically active. The apparent diffusion coefficient of BEB-Fe was increased with increasing ferrate fractions. (C) 2014 Elsevier Ltd. All rights reserved.