In this paper, flower-like Bi2Se3 nanostructures consisting of intercrossed nanosheets networks have been synthesized via a facile hydrothermal technique and applied to the protein electrochemistry for the first time. The prepared Bi2Se3 nanostructures were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscopy (TEM). The direct electrochemistry of hemoglobin (Hb) has been achieved by immobilizing Hb on the prepared Bi2Se3 nanostructures and Nafion (NO modified glassy carbon electrode. Bi2Se3 nanostructures show significant promotion to the direct electron-transfer of Hb. The immobilized Hb retained its biological activity well and shows high catalytic activity to the reduction of hydrogen peroxide (H2O2). Under the optimal experimental conditions, the catalytic currents are linear to the concentrations of H2O2 in the range of 2.0 x 10(-6) to 1.0 x 10(-4) M. The corresponding detection limits are 6.3 x 10(-7) M. The prepared flower-like Bi2Se3 nanostructures provide an alternative matrix for protein immobilization and biosensor preparation. (C) 2012 Elsevier Ltd. All rights reserved.