The present report presents results from the fabrication, structural, and optical characteristics of sub-100 nm thermal chemical vapor deposition-grown silicon-oxycarbide (SiC x O y ) nanowire (NW) arrays fabricated by e-beam lithography and reactive-ion-etching. The composition of SiC x O y materials follows closely the silicon-oxycarbide stoichiometry [SiC x O 2(1Àx) , (0 , x , 1)] as observed by compositional and structural analysis. The corresponding structural and bonding evolution of SiC x O y are well-correlated with changes in their optical properties, as demonstrated by the linear dependence of their optical gap and refractive index with [Si-C]/[Si-O] bond-area ratio. By virtue of these advantages, properly tailored SiC x O y NWs were fabricated, exhibiting strong room-temperature visible photoluminescence (PL) through engineering of [Si-C]/[Si-O] bonds. The current studies focused on the thermal-oxidation and excitation intensity behavior of SiC x O y NWs revealed their very good stability, as their luminescence characteristics remain unchanged upon annealing in oxygen ambient (250°C), while the PL intensity dependence on the excitation power-density exhibited a linear increase up to ;800 W/cm 2 .