An annealing method has been reported for silicon anode based on polyvinylidene fluoride (PVDF) binder. High initial coulombic efficiency of 75.6% and a stable reversible capacity of 715.6mAhg−1 for 50 cycles have been obtained after annealing process. Such improvements are attributed to the enhanced cohesive ability of PVDF and the compact morphology of the electrode reconstructed by annealing, which improves the electronic contacts of silicon particles and stabilizes the electrode structure effectively. It is demonstrated that such annealing method is very economic and effective for performance improvement of silicon anode.