Electrochemical behavior of hemin on p-GaAs(1 0 0) electrodes was examined by cyclic voltammetry (CV) and impedance spectroscopy (EIS) in phosphate buffer solutions (PBS) at pH 7.45. CV investigations in 0.6 mM hemin in PBS revealed a pair of reversible peaks at -0.44 and -0.32 V vs. SCE resulting in stable adsorbed species. EIS spectra analysis pointed out that these adsorbed species bring significant changes in the semiconductor surface state population and the potential drop distribution between the semiconductor space charge region and the Helmholtz layer. (C) 2010 Elsevier Ltd. All rights reserved.