Phosphorus-containing carbon has been prepared by the pyrolysis of phenolic resin containing chemically bonded phosphorus atoms, which is synthesized through the esterification of phenolic hydroxyl group by phosphoric acid. The electrochemical insertion of lithium in as-prepared carbon is also investigated. It is found that, at a pyrolysis temperature of 500°C, the addition of phosphoric acid in the precursor lowers the reversible capacity of the resultant carbon, but at 900°C, the addition of phosphoric acid in the precursor resin increases the reversible capacity of resultant carbon. Especially, the phosphorus-containing carbon prepared by the above method at 900°C gives a capacity beyond the theoretical value of graphite and reasonable discharge/charge curves. The phosphorus-containing carbon prepared by the pyrolysis at 500°C shows a similar electrochemical behavior to that of pure carbon and the effect of phosphorus atoms is little. Its reversible capacity is mainly determined by the content of hydrogen atoms rather than phosphorus atoms. However, at a relatively high pyrolysis temperature, 900°C, more phosphorus atoms are bonded with carbon atoms and are introduced to the microcrystallite structure of carbon. Hence, phosphorus element exerts a strike effect on the electrochemical behavior of carbon and, because of its different electronic effect from carbon element, more lithium species are inserted into carbon matrix.