The aim of this research is to realize the constructions of Mn—O—C bonds by covering the coal tar pitch based carbon materials on the surface of MnO. The formations of Mn—O—C bonds play the main role to construct the conductive network so as to diminish the interfacial resistance, which causes that the prepared MnO@C materials possesses the excellent electrochemical performances such as high Li+ storage capacity, excellent rate performances and long cycle performances. Based on the hydrothermal method, the Mn3O4@C precursors are synthesized by using the water soluble coal tar pitches (WSP) and KMnO4. The MnO@C materials are synthesized by the carbothermic reduction reaction methods using the Mn3O4@C precursors. The morphologies, surface characteristics and detailed structures of MnO@C materials are verified by the TEM, SEM, XPS, XRD and Raman measurements. TEM and SEM results indicate that plenty of oxygen-containing functional groups existing in the WSP possess the interactions with the Mn2+ of MnSO4 solution, which is able to facilitate the formations of cores which are beneficial to accelerate the formations and uniformly growing of nano particles in MnO@C materials. Formations of nano particles are also play the role to enhance the electrochemical performances of MnO@C materials. The XRD, Raman and XPS results indicate that a lot of Mn—O—C bonds formed between the surface of MnO and carbon materials in the MnO@C materials. The electrochemical performances of MnO@C materials were evaluated by cyclic voltammetry, charge-discharge and electrochemical impedance spectroscopy measurements.As a result, it is found that MnO@C shows the storage capacity at 606.47 mAh/g after cycling charge-discharge 100 cycles at a current density of 0.1 A/g. Although the current density was increased to 0.5 A/g, the MnO@C composite materials still show the storage capacity at 293.83 mAh/g after 400 cycles. Additionally, the fact that MnO@C materials have the tremendous rate performances was also determined in these presented studies. In summarization, the WSP were successfully prepared mixed acid methods using the coal tar pitches from ANGANG STEEL. The Mn3O4@C precursors were successfully synthesized by using WSP and KMnO4. The MnO@C composite materials are successfully synthesized by using the Mn3O4@C precursors. The electrochemical evaluations show that covering the carbon materials on the surface of MnO is the effective way to enhance the electrochemical performances of MnO, for covering the carbon materials on the surface of MnO provides the active sides not only, but also can restrain the volume expansion of MnO in charge-discharge process. Especially, the constructions of Mn—O—C bonds between the carbon materials and MnO play the main role to enhance the transfer abilities of electronic and ions between the carbon materials and MnO, which proves the electrode reaction kinetics. Considering the fact that coal tar pitches are the bulk commodities, the Mn3O4@C should have the significant cost advantage in fabrication processes.