A novel CuO negative electrode with network-like architectures was fabricated on copper substrate by a simple solution-immersion step and subsequent heat treatment, which avoids the use of binder and conducting agent that necessary to the conventional electrode-preparation process. The as-prepared CuO electrodes exhibit not only high reversible capacity but also long cycling life, high rate capability in Li ion batteries. The result of this approach creates a new and attractive negative electrode with good electrochemical performance, which is simple, mild conditions, low cost, and easy control. It also opens a pathway for the application of other nanostructured materials of transition metal oxides in lithium ion batteries.