A single crystalline K0.33W0.944O3 nanowires were synthesized at 450°C in air with the help of a simple and convenient method, vapor-solid (VS) process. Raman scattering used in the study helped to probe the crystal properties of the nanowires. Field-emission scanning electron microscope (FESEM) measured the electron field emission measurement of potassium tungsten bronze nanowire film and also observed the morphology of the as-grown samples. It was demonstrated that tungsten bronze nanostructures were capable of being synthesized into nanorods, nanowires, or nanosheets with the change in heating temperature. Polarized Raman mapping of individual nanowires showed the single crystallinity of the nanowires. The dynamic growth process of nanowires was monitored by SEM. The potassium tungsten bronze nanostructures obtained can find role in many applications including emission electron sources and displays (FED).