Two types of SnO2 nanofibers were prepared by electrospinning and calcination of polyvinyl acetate/stannic chloride pentahydrate and polyvinyl pyrrolidone/stannic chloride pentahydrate precursors, respectively. Due to the different properties of polymer solutions and different decomposition mechanisms during calcination, the as-prepared SnO2 nanofibers showed different morphologies and crystal structures. As a result, they exhibited different performance when used as lithium-ion battery anodes and photocatalysts. In the lithium-ion battery test, the SnO2 nanofibers obtained from polyvinyl acetate/stannic chloride pentahydrate precursor showed a higher reversible specific capacity (871 mAh g(-1)) and better cycling performance (574 mAh g(-1) after 20th cycles) because their cobweb-like structure and polycrystalline nature had better ability to accommodate the volume changes of SnO2. On the other hand, SnO2 nanofibers derived from polyvinyl pyrrolidone/stannic chloride pentahydrate precursor exhibited higher photocatalytic degradation of methylene blue (56 %) even at a low concentration of (10(-5) M, 50 ml) because they provided higher surface area for absorbing and degrading methylene blue.