In this novel paper, a technique for hydrogen production route of CaO sorption-enhanced methane steam reforming (SEMSR) thermally coupled with chemical looping combustion (CLC) was presented (CLC-SEMSR), which perceived as an improvement of previous methane steam reforming (MSR) thermally coupled with CLC technology (CLC-MSR). The application of CLC instead of furnace achieves the inherent separation of CO2 from flue gas without extra energy required. The required heat for the reformer is provided by thermally coupling CLC. The addition of CaO sorbents can capture CO2 as it is formed from the reformer gas to the solid phase, displacing the normal MSR equilibrium restrictions and obtaining higher purity of H-2. The Aspen Plus was used to simulate this novel process on the basis of thermodynamics. The performances of this system examined included the composition of reformer gas, yield of reformer gas (Y-Rg), methane conversion ((M)), the overall energy efficiency (), and exergy efficiency (phi) of this process. The effects of the molar ratio of CaO to methane for reforming (Ca/M) in the range of 0-1.2, the molar ratio of methane for combustion to methane for reforming (M(fuel)/M) in the range of 0.1-0.3, and the molar ratio of NiO to methane for reforming (Ni/M) in the range of 0.4-1.2 were investigated. It has been found to be favored by operating under the conditions of Ca/M=1, M(fuel)/M=0.2, and Ni/M=0.8. The most excellent advantage of CLC-SEMSR was that it could obtain higher purity of H-2 (95%) at lower operating temperature (655 degrees C), as against H-2 purity of 77.1% at higher temperature (900 degrees C) in previous CLC-MSR. In addition, the energy efficiency of this process could reach 83.3% at the optimal conditions. Copyright (c) 2014 John Wiley & Sons, Ltd.