We report on the first studies of the optical properties of MBE-grown ZnTe nanowires (NWs). The growth of ZnTe NWs was based on the Au-catalyzed vapour–liquid–solid mechanism and was performed on (001), (011), or (111)B-oriented GaAs substrates. Investigated NWs have a zinc-blende structure, the average diameter of about 30 nm, and typical length between 1 and 2 μm. Their growth axes are oriented along <111>-type directions of the substrate. The structural characterization of the NWs was performed by means of X-ray diffraction, using the synchrotron radiation corresponding to the wavelength of CuKα1 radiation W1 beamline at Hasylab DESY). The macro-Raman spectra of either as-grown NWs on GaAs substrate or of NWs removed from substrate and deposited onto Si were collected at temperatures from 15 K to 295 K using Ar+ and Kr+ laser lines. Strong enhancement of ZnTe-related LO-phonon structure was found for an excitation close to the exciton energy. Our studies revealed also the presence of small trigonal Te precipitates, typical of tellurium compounds.