Li6Zr2O7 nanofibers were synthesized by a simple electrospinning technique. The thermal decomposition behavior, crystal structure, micromorphology, and electrical conductivity of the as-prepared Li6Zr2O7 nanofibers were characterized. The results show that Li6Zr2O7 nanofibers were of pure phase after calcined at 750 degrees C for 1 h. In addition, the as-prepared Li6Zr2O7 nanofibers reveal high conductivity in the measured temperature region, which can be attributed to the huge surface and nanosize effect of the nanofiber electrolyte. Moreover, we provide a general method to improve the conductivity of Li-ion solid electrolyte.