We study optimal operation of a post-combustion CO2 capturing process where optimality is defined in terms of a cost function that includes energy consumption and penalty for released CO2 to the air. Three different operational regions are considered. In region I, with a nominal flue gas flowrate, there are two optimally unconstrained degrees of freedom (DOFs) and the corresponding best self-optimizing controlled variables (CVs) are found to be the CO2 recovery in the absorber and the temperature at tray no. 16 in the stripper. In the region II, with an increased flue gas flowrate, the heat input is saturated and there is one unconstrained DOF left. The best CV is temperature at tray no. 13 in the stripper. In region III, when the flue gas flowrate is further increased, the process reaches the minimum allowable CO2 recovery of 80% and there is no unconstrained DOF. We have then reached the bottleneck and a controller is needed to adjust the feed flowrate to avoid violating this minimum. The exact local method and the maximum gain rule are applied to find the best CVs in each region. (C) 2011 Elsevier B.V. All rights reserved.