Aniline doped with polyvinyl sulphonate (PV-SO3-) was electropolymerised on screen printed carbon (SPCE) and glassy carbon (GCE) electrodes. Then nano-structured polystyrene (PSN) latex beads functionalised with amine (PSNP-NH2) and sulphate (PSNP-OSO3-) were self-assembled on the modified SPCE and GCE. The resultant polyaniline nanocomposites (PANI vertical bar PSNP-NH2 or PANI vertical bar PSNP-OSO3-) were characterised by cyclic voltammetry (CV), UV-vis spectroscopy and scanning electron microscopy (SEM). Brown-Anson analysis of the multi-scan rate CV responses of the various PANI films gave surface concentrations of the order of 10(-8) mol cm(-2). UV-vis spectra of the PANI films dissolved in dimethyl sulphoxide showed typical strong absorbance maxima at 480 and 740 nm associated with benzenoid pi-pi* transition and quinoid excitons of polyaniline, respectively. The SEM images of the PANI nanocomposite films showed cauliflower-like structures that are <100 nm in diameter. When applied as electrochemical nitrite sensor, sensitivity values of 60, 40 and 30 mu A/mM were obtained for electrode systems containing PANI vertical bar PSNP-NH2, PANI and PANI vertical bar PSNP-SO3-, respectively. The corresponding limits of detection of the sensors were 7.4, 9.2 and 38.2 mu M NO2-. (C) 2009 Elsevier Ltd. All rights reserved.