Highly oriented single crystal antimony nanowire arrays have been synthesized within anodic aluminum oxide (AAO) template by pulsed electrodeposition. Thermal behavior and oxidation analysis of the antimony nanowires have been investigated by means of thermogravimetry and differential scanning calorimetry in Ar and air atmosphere, respectively. Compared to bulk antimony, the antimony nanowires exhibit a lower sublimation temperature at 496.4°C. Evident oxidation of the Sb nanowires occurs at 429.8°C in air atmosphere and α-Sb2O4 nanowires have been obtained as the oxidation product. The results indicate that the sublimation and the oxidation of the antimony nanowires in the AAO template is a slow multi-step process. The present results are of relevance when processing antimony nanowries for thermoelectric applications at high temperatures.