Tip-enhanced Raman spectroscopy is combined with polarization angle-resolved spectroscopy to investigate the nanometre-scale structural properties of core-shell silicon nanowires (crystalline Si core and amorphous Si shell), which were synthesized by platinum-catalyzed vapor-liquid-solid growth and silicon overcoating by thermal chemical vapour deposition. Local changes in the fraction of crystallinity are characterized for those silicon nanowires at an optical resolution of about 300 nm. Furthermore, we are able to resolve the variations in the intensity ratios between the crystalline Si and the amorphous Si Raman peaks by applying tip-enhanced Raman spectroscopy, at sample positions being eight nanometers apart. The local crystallinity revealed using confocal Raman spectroscopy and tip-enhanced Raman spectroscopy agree well with the high-resolution transmission electron microscopy measurements. Additionally, the polarizations of Raman scattering and the photoluminescence signal from the tip-sample nanogap are explored by combining polarization angle-resolved emission spectroscopy with tip-enhanced optical spectroscopy. Our work demonstrates the significant potential of resolving local structural properties of Si nanomaterials at the sub-10 nanometer scale using tip-enhanced Raman techniques.