In this study, a facile method is proposed to fabricate biocompatible TiN nanorod arrays through solvent-thermal synthesis and subsequent nitridation in ammonia atmosphere. The TiN nanorod arrays are potential excellent nanostructured electrodes owing to their good electronic conductivity and large surface area. These nanostructured electrodes not only deliver superior electrocatalytic activity (the limit of detection, LOD is 0.5 μM) and highly selective sensing towards H(2)O(2), but also exhibit excellent biocompatibility with horseradish peroxidase (HRP) in a highly sensitive enzymatic biosensor for H(2)O(2) (the LOD can reach to 0.05 μM). Furthermore, a novel biocatalytic cathode based Li air fuel cell (bio-Li-air fuel cell) is explored based on the combination of TiN nanorod arrays and laccase (LAC) for electrochemical energy conversion. These results demonstrate that TiN nanorod arrays can be served as excellent nanostructured electrodes for multifunctional bioelectrochemical applications. Copyright © 2011 Elsevier B.V. All rights reserved.