BACKGROUND: Carbon nanotube (CNT) fiber directly spun from an aerogel has a unique, well-aligned nanostructure (nano-pore and nano-brush), and thus provides high electro-catalytic activity and strong interaction with glucose oxidase enzyme. It shows great potential as a microelectrode for electrochemical biosensors. RESULTS: Cyclic voltammogram results indicate that post-synthesis treatments have great influence on the electrocatalytic activity of CNT fibers. Raman spectroscopy and electrical conductivity tests suggest that fibers annealed at 250 degrees C remove most of the impurities without damaging the graphite-like structure. This leads to a nano-porous morphology on the surface and the highest conductivity value (1.1 x 10(5) S m(-1)). Two CNT fiber microelectrode designs were applied to enhance their electron transfer behaviour, and it was found that a design using a 30 nm gold coating is able to linearly cover human physiological glucose level between 2 and 30 mmol L(-1). The design also leads to a low detection limit of 25 mu mol L(-1). CONCLUSIONS: The high performance of CNT fibers not only offers exceptional mechanical and electrical properties, but also provides a large surface area and electron transfer pathway. They consequently make excellent bioactive microelectrodes for glucose biosensing, especially for potential use in implantable devices. (C) 2011 Society of Chemical Industry