The cobalt carbide (Co2C) innovatively prepared from Co-Mn layered double hydroxide (CoMn LDH) has been investigated and evaluated toward its alternative synthesis conditions and different catalytic performances. Along with various characterization techniques, the preparation basically contains four steps (synthesis of CoMn LDH, calcination, reduction, and crystallization) that transform CoMn LDH to CoMn spine] and then to Co2C. Catalyst evaluation toward toluene pyrolysis was conducted. The sample with Co2C exhibited almost 100% conversion rate of toluene, where the resulting hydrogen yield (similar to 1.8%) is 6 times more than that of the blank test by using silica sand (similar to 0.3%), realizing the full transfer of hydrogen element from toluene to hydrogen molecule. Furthermore, based on the textural analysis and density functional dispersion correction calculation, which theoretically explained the easy accessibility of toluene to the crystal surface of Co2C(001) with a relatively high adsorption energy (about -280 kJ mol(-1)), it suggested that Co2C may expand more extensive applications in the field of catalysis.