The objective of this paper is to assess the economic advantages of an innovative solvent for CO2 capture on state-of-the-art solvents. The CESAR-1 solvent, which is an aqueous solution of 2-amino-2-methyl-propanol (AMP) and piperazine (PZ), is applied both to advanced supercritical pulverised (ASC) coal and natural gas combined cycle (NGCC) power plants with post-combustion CO2 capture units. The methodology includes process model developments using commercial simulation programs, which determine the thermodynamic properties of the selected power plants and the performance of the CO2 capture units. The results show that the techno-economic benefit of CESAR-1 versus MEA is more significant for ASC than that for NGCC due to a higher concentration of CO2 in the flue gas. This follows from the fact that the switch from MEA to CESAR-1 solvents reduces the electricity cost by 4.16€/MWh in the case of the ASC plant compared to 0.67€/MWh in connection with the proposed NGCC plant. Based on the above figures, we can conclude that CESAR-1 reduces the cost of CO2 avoided compared to MEA by 6€/t CO2 and 2€/t CO2 for the selected ASC and NGCC plants respectively. In view of that, the techno-economics can be improved if the CO2 capture plant is designed to operate using the CESAR-1 absorption technology due to a reduction in the regeneration energy and the solvent recirculation rate (considering its higher CO2 net capacity). However, the variable costs of running the capture plant are higher for the CESAR-1 solvent due to the higher cost of the amines.