Novel plum-branch-like carbon nanofibers (CNFs) decorated with SnO2 nanocrystals have been synthesized by electrospinning and subsequent thermal treatment in an Ar/H2O atmosphere. The morphologies of the as-synthesized SnO2/CNF composites and the contents of carbon and SnO2 can be controlled by adjusting the heat treatment temperature. It is proposed that the growth of SnO2/CNF composites follows the outward diffusion of tin composites from the as-spun tin composite/polyacrylonitrile (PAN) nanofibers, pyrolysis of PAN and oxidation of tin composites, and then formation of SnO2 nanocrystals around the CNFs. This novel 1D SnO2/CNF composite may have potential application in nanobatteries, nano fuel cells, and nanosensors. A preliminary result has revealed that the SnO2/CNF composite presents favourable electrochemical performance in lithium-ion batteries.