The catalytic decomposition of CH4 using low cost and non-toxicity Fe-based catalysts is a prospective method for H2 production. The regeneration process of iron-based catalysts involves CO2 emission and incomplete conversion of carbon deposition. In this work, a novel catalytic decomposition of CH4/regeneration process was proposed using the Ce-doped Fe/CaO-Ca12Al14O33 catalyst for H2 production. To remove the carbon deposition in the catalyst, the regeneration stage includes four steps: solid carbon production by vibratory separation, steam gasification of residual carbon deposition to produce H2 where CO2 is captured by CaO to form CaCO3, calcination of CaCO3 to produce CaO and pure CO2, methanol production by CO2 and H2 from carbon deposition gasification. The effects of Ce doping on the catalysis/regeneration performance of Fe/CaO-Ca12Al14O33 catalysts were studied, and the Ce-doped Fe/CaO-Ca12Al14O33 catalyst was compared with Cu-, Zn-, and Mn- doped Fe/CaO-Ca12Al14O33 catalysts. The solid carbon obtained from the catalytic decomposition of CH4/regeneration cycles was characterized. The Ce-doped Fe/CaO-Ca12Al14O33 catalyst shows excellent catalysis, CO2 capture, and stability performance in the catalytic decomposition of CH4/regeneration cycles. The average CH4 conversion is 90.02% in the first cycle, which decreases to 80.01% after 8 cycles. Carbon nanotubes are the main forms of obtained solid carbon with the favorable pore structure. The doping of Ce improves the effective adsorption sites for CH4 and CO2. Carbon deposition in the catalyst is efficiently removed by steam gasification. In addition, CeO2 promotes the electron transfer, oxygen vacancy generation, and Fe3C decomposition, which leads to superior catalytic performance and resistance to deactivation of the catalyst. The CeO2-doped Fe/CaO-Ca12Al14O33 catalyst is promising for H2 production via catalysis/regeneration cycles.