B doping plays an important role in improving the conductivity and electrochemical properties of Si anodes for Li-ion batteries. Herein, we developed a facile and massive production strategy to fabricate C-coated B-doped Si (B-Si@C) nanorod anodes using casting intermediate alloys of Al-Si and Al-B and dealloying followed by C coating. The B-Si@C nanorod anodes demonstrate a high specific capacity of 560 mAg-1, with a high initial coulombic efficiency of 90.6% and substantial cycling stability. Notably, the melting cast approach is facile, simple, and applicable to doping treatments, opening new possibilities for the development of low-cost, environmentally benign, and high-performance Li-ion batteries.