This study investigates the crucial role of Carbon Capture and Storage (CCS) technology in mitigating CO2 emissions from Poland’s power systems, which is essential not only for meeting climate targets but also for maintaining energy security in the country. Acknowledging natural gas as a transitional fuel, the focus is on evaluating the decarbonization potential of the natural gas combined cycle (NGCC) power plant. The NGCC with and without an amine-based carbon capture unit was modeled using IPSEpro (SimTech, version 7.0). It was found that the annual CO2 emission from 435.68 MWe (net) NGCC can be reduced from 1,365,501 tons (357.8 kgCO2/MWh) to 136,556 tons (42.9 kgCO2/MWh). On the other hand, the CCS reduced the net electric power of the NGCC from 435.68 MW to 363.47 MW and the net energy efficiency from 55.60% to 46.39%. Nonetheless, these results demonstrate the potential of using the amine-based CO2 capture technology in NGCC systems. This is especially important in the context of the decarbonization of the Polish power system.