Novel PbO@C composite is synthesized through an optimized mechano-chemical method and used as negative active materials for enhanced performance of lead-carbon battery. Mechanical ball-milling of solid lead acetate, sodium hydroxide and carbon additives (Vulcan-72) would generate uniform composite of lead oxide and carbon (PbO@C) via chemical reactions and mechanical dispersion. The constant mechanical impact and friction during ball-milling leads to lattice distortion and enables intimate connection between Pb and C in the synthesized PbO@C composite, which is proved to be critical for the enhanced battery performance. The specific capacity is higher than battery with direct addition of carbon as additives (126.5 vs. 118.9 mAh g−1), and the cycle performance under high rate partial-state-of-charge duty is also improved. Batteries with the utilization of PbO@C composite accomplished 15119, 11296, 9882, 8336 and 7038 cycles within five consecutive cycle-sets of cycle test, with a decreasing rate of 19.12%, which was drastically lower than battery with direct addition of VC 72 (30.14%). The proposed research provides a promising strategy for feasible synthesis of negative active materials for lead-carbon batteries.