We experimentally investigate the stabilization of the anatase phase of Ti1-xSnxO2 (x < 0.5) nanofibers when synthesized by an electrospinning method. The as-spun nanofibers became nano-grained, polycrystalline nanofibers after calcination and the diameters of the nanofibers depend on Sn content. Stabilization of the anatase phase in Ti-rich compositions and incorporation of Sn ions were confirmed by X-ray diffraction, Raman, X-ray absorption near-edge structure, and photoluminescence (PL) spectroscopies. Results from the PL study also demonstrated the tunable nature of the optical properties, with the emission maximum shifting towards higher wavelength with increasing Sn concentration.