Titanate nanotubes (TiNT) surface modified with (3-aminopropyl)trimethoxysilane were employed as a support for covalent immobilization of horseradish peroxidase (HRP) by using 1,4-benzoquinone as a coupling agent. Composite film-electrodes consisting of HRP-modified TiNT embedded into the porous carbon powder/Nafion matrix were fabricated and their applicability in direct bioelectrocatalytic reduction of H2O2 and H2O2 biosensing were investigated. An efficient direct electron transfer between the immobilized HRP molecules and the electrode was observed in the presence of H2O2 at potentials lower than 600 mV (vs. Hg/Hg2Cl2/3.5 M KCl). For the HRP-TiNT-modified electrodes polarized at 0 mV, a linear dependence of the bioelectrocatalytic current on the concentration of H2O2 was observed up to the concentration of H2O2 equal to 10 p,M, with the sensitivity of (1.10 +/- 0.01) AM(-1) cm(-2) and the detection limit of 35 nM. (C) 2011 Elsevier Ltd. All rights reserved.