In this work, two layered double hydroxides, Zn2Cr-ABTS and Zn2Al-Fe(CN)6 LDH, have been synthesized and characterized by X ray diffraction and FTIR spectroscopy to confirm the intercalation of redox anions between inorganic layers. These redox active hybrid materials have been used to electrically connect laccase (Lac) and glucose oxidase (GOx) in biofuel cell devices. Co-immobilization of hybrid LDH and enzymes has been performed by entrapment in electropolymerized films of polypyrrole deposited on porous carbon tubular electrodes. Lac/Zn2Cr-ABTS cathodic electrode allows the electro-enzymatic reduction of O2, whereas the anodic electrode GOx/Zn2Al-FeIII(CN)6was used for the electro-enzymatic oxidation of glucose. With a two compartment configuration, a maximum power density of 45 μW cm−2was obtained at 0.2 V.