The fossil fuel power generation sector is facing critical decisions to significantly reduce CO2 emissions by implementing carbon capture technologies at industrial scale for transition to low carbon economy. This paper assesses the usage of reactive absorption/adsorption systems for post-combustion CO2 capture from Natural Gas Combined Cycle (NGCC) power plants. As reactive gas–liquid absorption system assessed for post-combustion CO2 capture, the alkanolamine-based gas–liquid absorption was evaluated (MDEA was considered as illustrative example). As reactive gas–solid adsorption system, the innovative Calcium Looping (CaL) method was considered. The work evaluates how chemical absorption/adsorption influence the techno-economic performances of NGCC power plants. As benchmark option used to quantify the carbon capture energy and cost penalties, NGCC plant without CO2 capture was considered. The post-combustion carbon capture options have at least 90% carbon capture rate. As the results show, CaL concept exhibits improved environmental performances (e.g. >98 vs. 90% carbon capture rate) and economic indicators (e.g. 969 vs. 1238 €/kW net power as specific capital investment, 42.82 vs. 46.24 €/MWh as O&M costs, 56.91 vs. 66.12 €/MWh as electricity cost etc.) compared to MDEA case.