The preparation of high-purity and -quality gallium nitride nanowires is accomplished by a catalytic growth using gallium and ammonium. A series of catalysts and different reaction parameters were applied to systematically optimize and control the vapor−liquid−solid (VLS) growth of the nanowires. The resulting nanowires show predominantly wurtzite phase; they were up to several micrometers in length, typically with diameters of 10−50 nm. A minimum nanowire diameter of 6 nm has been achieved. Temperature dependence of photoluminescence spectra of the nanowires revealed that the emission mainly comes from wurtzite GaN with little contribution from the cubic phase. Moreover, the thermal quenching of photoluminescence was much reduced in the GaN nanowires. The Raman spectra showed five first-order phonon modes. The frequencies of these peaks were close to those of the bulk GaN, but the modes were significantly broadened, which is indicative of the phonon confinement effects associated with the nanoscale dimensions of the system. Additional Raman modes, not observed in the bulk GaN, were found in the nanowires. The field emission study showing notable emission current with low turn-on field suggests potential of the GaN nanowires in field emission applications. This work opens a wide route toward detailed studies of the fundamental properties and potential applications of semiconductor nanowires.