The Se/Te alloys nanorods have been synthesized through spontaneous oxidation of NaHE (E = Se and Te) by dissolved oxygen at room temperature. Phase structures and morphologies of the Se/Te products are investigated by XRD, EDS, SEM, and TEM. The composition of Se/Te alloys could be tuned via simply changing the value of n (n denoted as molar ratio of the starting reagent Se to Te). In order to obtain pure Se/Te alloys nanorods, the value of n should be higher than 3. Otherwise, by-product t-Te would be formed. A possible nucleation and growth mechanism of the Se/Te nanorods was discussed.