An initiator is applied to synthesize single-walled carbon nanotube/polyaniline composite nanofibers for use as high-performance chemosensors. The composite nanofibers possess widely tunable conductivities (10(-4) to 10(2) S/cm) with up to 5.0 wt % single-walled carbon nanotube (SWCNT) loadings. Chemosensors fabricated from the composite nanofibers synthesized with a 1.0 wt % SWCNT loading respond much more rapidly to low concentrations (100 ppb) of HCl and NH(3) vapors compared to polyaniline nanofibers alone (120 s vs 1000 s). These nanofibrillar SWCNT/polyaniline composite nanostructures are promising materials for use as low-cost disposable sensors and as electrodes due to their widely tunable conductivities.