We report the characterization of mixed oxides nanocomposite nanofibers of (1 x) ZnO-(x)SnO2 (x ≤ 0.45) synthesized by electrospinning technique. The diameter of calcined nanofibers depends on Sn content. Other phases like SnO, ZnSnO3, and Zn2SnO4 were absent. Photoluminescence studies show that there is a change in the blue/violet luminescence confirming the presence of Sn in Zn-rich composition. Present study shows that the crystalline nanocomposite nanofibers with stoichiometry of (1 x)ZnO-(x)SnO2 (x ≤ 0.45) stabilize after the calcination and possess some morphological and optical properties that strongly depend on Sn content.