Hydrogen is a potential clean energy and hydrogen production technologies are important research topics that can lead into a new energy era. Coal is a cheap and abundant energy resource compared to expensive and limited petroleum. Synthesis gas produced from coal gasification can be used to produce hydrogen through water gas shift (WGS) reaction (CO + steam ↔ CO2 + H2) and purification procedures. The conventional route includes pressure swing adsorption (PSA) processes to produce a high purity hydrogen product gas. PSA processes can also be designed to produce a CO2 by-product at ambient pressure. This study discusses the "Thermal Swing Sorption Enhanced Reaction (TSSER)" which simultaneously carries out the WGS reaction and the separation of CO2 from the reaction zone by using a novel CO2 chemisorbent in a single unit operation. The new process produces a fuel-cell grade hydrogen (< 10 ppm CO) and compressed CO2 as a by-product gas. The simultaneous removal of CO2 during WGS reaction circumvents the thermodynamic limitation and shifts equilibrium to the right resulting in the enhancement of the extent of the forward reaction. As a result, a pure hydrogen stream can be directly produced, and the process is simpler and potentially more economical than the conventional WGS. Sorption enhanced WGS reaction was tested experimentally and confirmed to produce high purity hydrogen. The thermal swing concept was used for column regeneration and production of compressed CO2. A five-step continuous process was tested by simulation. High net conversion of CO to hydrogen product, high CO2 recovery, and efficient column regeneration was achieved.