A facile, efficient, environmentally benign route has been reported to synthesize toast-like porous carbon (TPC) materials via one-step solid reaction between LiH and CaCO3 powder mixture at 600 oC. The release of gas from the reaction process plays a key role in the formation of toast-like micro-/meso- porous structure. As an anode material for Li ion batteries, the as-synthesized TPC exhibits ultrahigh specific capacity of 1016 mAh g-1 (after 300 cycles at 200 mA g-1), superior rate capability (730 mAh g-1 at 1000 mA g-1), and excellent cycling ability (up to 1400 cycles at 4000 mA g-1). The exceptional lithium storage performance of TPC could be attributed to its novel hierarchical structure and good structural stability, which not only provide high accessible surface area for charge storage, but also act as reservoirs for lithium storage. This chemical reaction route opens new avenues for synthesizing porous carbon materials for energy storage application.