A method for simply and controllably modifying the surface of polyaniline nanofibres is described. The technique can be used to attach substituents bearing both acid and amine functional groups, making the materials suitable for further modification. Acid/amine functionalisation is achieved by a simple reflux reaction and therefore is a quick and easily scalable process. The modified nanofibres maintain their ability to switch between different states displaying distinctly different properties, thus making them suitable for adaptive sensing applications. As an example, we demonstrate how biomolecules can be attached to these functionalised nanofibres, to produce conducting polymer-based biosensors. © 2010 Materials Research Society.