Several experiments have demonstrated that the chemical-looping with oxygen uncoupling (CLOU) provides an effective technological pathway for high-efficiency low-cost carbon dioxide capture when particulate coal serves as the fuel. In this paper, complete process-level modeling of CLOU process is established in ASPEN Plus based on a series of detailed experiments. The heat content of fuel and air reactors and air/flue gas heat exchangers is carefully examined. It is shown that the established model provides results that are in excellent agreement with the experiments for the flue stream contents of both the reactors, oxygen carrier conversion kinetics, and the overall performance of the CLOU process. Four scaled-up cases are also carried out to investigate the influence of increase in the coal and oxygen carriers feeding. Additionally, three different types of coal as the solid fuel are also investigated to determine their effect on the CO2 concentration in the flue stream and on the overall energy performance.