We report on the synthesis of quasi-1D W5O14 crystals using NiI2 as a growth promoter. Photoelectron spectroscopy revealed the metallic conductivity of the W5O14 nanowires, which was also confirmed by direct-transport measurements on a double-stranded nanowire. Scanning electron microscopy and transmission electron-diffraction data are correlated with details of crystal growth revealing the possible mechanism of the formation of this rarely synthesized phase, which was reported as a homogeneous phase only in 1978 by McColm et al., and in the meantime has been declared as a compound that is rare.