Catalytic decomposition of methane (CDM) is a promising technology for producing COx-free hydrogen and nano-carbon, meanwhile it is a prospective substitute to steam reforming of methane for producing hydrogen. The produced hydrogen is refined and can be applied to the field of electronic, metallurgical, synthesis of fine organic chemicals and aerospace industries. However, the CDM for COx-free hydrogen production is still in its infancy. The urgent for industrial scale of CDM is more important than ever in the current situation of huge COx emission. This review studies CDM development on Ni-based, noble metal, carbon and Fe-based catalysts, especially over cheap Fe-based catalyst to indicate that CDM would be a promising feasible method for large hydrogen production at a moderate cheap price. Besides, the recent advances in the reaction mechanism and kinetic study over metal catalysts are outlined to indicate that the catalyst deactivation rate would become more quickly with increasing temperature than the CDM rate does. This review also evaluates the roles played by various parameters on CDM catalysts performance, such as metal loading effect, influences of supports, hydrogen reduction, methane reduction and methane/hydrogen carburization. Catalysts deactivation by carbon deposition is the prime challenge found in CDM process, as an interesting approach, a molten-metal reactor to continually remove the floated surface solid carbons is put forwarded in accordance to overcome the deactivation drawback. Moreover, particular CDM reactors using substituted heating sources such as plasma and solar are detailed illustrated in this review in addition to the common electrical heating reactors of fixed bed, fluidized bed reactors. The development of high efficiency catalysts and the optimization of reactors are necessary premises for the industrial-scale production of CDM.