Silicon is the most attractive anode material of all known host materials for lithium ion batteries because of its high theoretical lithium-insertion capacity up to 4200 mAh g-1, but it is difficult to be applied for its poor cyclability caused by the mechanical invalidation for the insertion of lithium ions. Nanosilicon/CMC/AB composite electrodes doped with WC were prepared by ball milling. The effect of the structure transformation of the doped electrode on the electrochemical behavior was systematically analyzed by X-ray diffraction. The mechanical properties of doped silicon electrode play an important role on its long-term electrochemical stability. The capacity retention could be maintained about 90% after 40 cycles. It was demonstrated that the cycling stability of the nanosilicon composite electrode could get a great promotion by WC doping. The intensification of the mechanical properties is critical to enhance the performance of the composite electrode.