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 MW_e (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.