Solvent-based post combustion capture (PCC) is a well-developed technology for CO2 capture from power plants and industry. A reliable model that captures the dynamics of the solvent-based capture process is essential to implement suitable control design. Typically, first principle models are used, however they usually require comprehensive knowledge and deep understanding of the process. System identification approach is adopted to obtain a model that accurately describes the dynamics between key variables in the process. The nonlinear autoregressive with exogenous (NARX) inputs model is employed to represent the relationship between the input variables and output variables as two Multiple-Input Single-Output (MISO) sub-models. The forward regression with orthogonal least squares (FROLS) algorithm is implemented to select an accurate model structure that best describes the dynamics within the process. The prediction performance of the identified NARX models is promising and shows that the models capture the underlying dynamics of the CO2 capture process.