Natural gas is an important source of energy. This article addresses the problem of integrating an existing natural gas combined cycle (NGCC) power plant with a carbon capture process using various solvents. The power plant and capture process have mutual interactions in terms of the flue gas flow rate and composition vs. the extracted steam required for solvent regeneration. Therefore, evaluating solvent performance at a single (nominal) operating point is not indicative and solvent performance should be considered subject to the overall process operability and over a wide range of operating conditions. In the present research, a novel optimization framework was developed in which design and operation of the capture process are optimized simultaneously and their interactions with the upstream power plant are fully captured. The developed framework was applied for solvent comparison which demonstrated that GCCmax, a newly developed solvent, features superior performances compared to the monoethanolamine baseline solvent.