We report intense red luminescence from mesoporous n+-Si(100) nanowires (NWs) and nanocrystal-decorated p-Si NWs fabricated using electroless metal assisted chemical (MAC) etching. n+-Si NWs are composed of a labyrinthine network of silicon nanocrystals in a random mesoporous structure. p-type Si(100) NWs exhibit solid core structure, with a surface roughness that contains surface-bound nanocrystals. Both mesoporous n+-Si NWs and rough, solid p-Si NWs exhibit red luminescence at ∼1.7 and ∼1.8 eV, respectively. Time-resolved photoluminescence (PL) measurements indicated long (tens of μs) radiative recombination lifetimes. The red luminescence is visible with the naked eye and the red light is most intense from mesoporous n+-Si NWs, which exhibit a red-shift in the emission maximum to 1.76 eV at 100 K. The red PL from monolithic arrays of p-type NWs with nanocrystal-decorated rough surfaces is comparatively weak, but originates from the surface bound nanocrystals. Significant PL intensity increase is found during excitation for mesoporous NWs. X-ray photoelectron spectroscopy identifies a stoichiometric SiO2 on the rough p-Si NWs with a SiOx species at the NW surface. No distinct oxide is found on the mesoporous NWs. The analysis confirms that long life-time PL emission arises from quantum confinement from internal nanoscale crystallites, and oxidized surface-bound crystallites, on n+- and p-Si NWs respectively.