Bi2S3 and Bi2S3/C nanocomposites prepared by high-energy mechanical milling were evaluated as electrode materials in lithium secondary batteries. For a Bi2S3/C nanocomposite, Bi2S3 nanocrystallites were well distributed in an amorphous carbon matrix. The reaction mechanism of the Bi2S3/C electrode was also examined during the first cycle. The Bi2S3/C nanocomposite anode showed superior electrochemical performance (ca. 500mAhg−1 and 85% of the capacity retention over 100 cycles).