1-D nanostructures are deemed to be important building blocks for future optical and optoelectronic nanodevices. We have used electrospinning methods to synthesize nanofibers and freestanding, non-woven nanofibers membranes of single phase yttrium titanate and ErxY2−xTi2O7 (x = 0–12 %) with diameters less than 150 nm and have characterized the physical, thermal and optical properties. We have demonstrated that such fibers can be synthesized at a relatively low cost and high production volume with a narrow diameter range. No clear phases are observed up to a calcination temperature of 700 °C and pyrochlore phase appear at 725 °C which are also confirmed by the TGA. Single pyrochlore phase is observed at temperatures greater than 900 °C. No other oxide phases are present.