Aniline doped with polyvinyl sulphonate (PV-SO 3 -) was electropolymerised on screen printed carbon (SPCE) and glassy carbon (GCE) electrodes. Then nano-structured polystyrene (PS NP) latex beads functionalised with amine (PS NP-NH 2) and sulphate (PS NP-OSO 3 -) were self-assembled on the modified SPCE and GCE. The resultant polyaniline nanocomposites (PANI|PS NP-NH 2 or PANI|PS NP-OSO 3 -) 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 π-π* 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 μA/mM were obtained for electrode systems containing PANI|PS NP-NH 2, PANI and PANI|PS NP-SO 3 -, respectively. The corresponding limits of detection of the sensors were 7.4, 9.2 and 38.2 μM NO 2 -. © 2009 Elsevier Ltd.