Raman spectroscopy is employed to characterize structural and phonon properties of GaP/GaNP core/shell nanowires (NWs) grown by molecular beam epitaxy on Si substrates. According to polarization-dependent measurements performed on single NWs, the dominant Raman modes associated with zone-center optical phonons obey selection rules in a zinc-blende lattice, confirming high crystalline quality of the NWs. Two additional modes at 360 and 397 cm(-1) that are specific to the NW architecture are also detected in resonant Raman spectra and are attributed to defect-activated scattering involving zone-edge transverse optical phonons and surface optical phonons, respectively. It is concluded that the formation of the involved defect states are mainly promoted during the NW growth with a high V/III ratio. ; Funding Agencies|Vetenskapsradet (Swedish Research Council) [621-2010-3815]; U.S. National Science Foundation [DMR-0907652, DMR-1106369]; Royal Government of Thailand Scholarship