Hemoglobin was immobilized in Mg2Al-Layered Double Hydroxides (LDH) by coprecipation method at pH 9.0. Interactions between lib and LDH particles were investigated by X-ray diffraction patterns, FTIR, UV-vis, circular dichroism, and fluorescence spectroscopies. Morphology and porosity of Mg2Al-Hb(cop) biohybrid are analyzed from SEM and TEM images and permeability measurement. The direct electron transfer of immobilized Hb was studied by cyclic voltammetry, and the electrocatalytic activity was evaluated at glassy carbon modified with this Mg2Al-Hb(cop), biohybrid. Even though the percentage of electroactive Hb was less than 2%, this bioelectrode showed a low detection limit (1.5 x 10(-8) M) and a very high sensitivity (37 A/M cm(2)) for the amperometric detection of H2O2.