Flexible operation has the potential to significantly improve the economic viability of post-combustion CO2 capture (PCC). However, the impact of disturbances from flexible operation of the PCC process is unclear. The purpose of this study was to investigate the effects of flexible operation in a PCC pilot plant by implementing step-changes for improved dynamic data reliability. The flexible operation campaign was conducted at the CSIRO PCC pilot plant at AGL Loy Yang using monoethanolamine (MEA) absorbent. The pilot plant was operated under a broad range of transient conditions (changing flue gas flow, liquid absorbent flow and steam pressure) to capture the dynamics of a PCC process during flexible operation. The study demonstrated that the dynamics of flue gas flow rate was faster than absorbent flow rate. The greatest CO2 removal% was achieved at the lowest flue gas flow rate or at the highest absorbent flow rate; however, the latter provided improved energy efficiency. The steam pressure parameter could adjust the temperature of all columns simultaneously which can be used to compensate for effects from ambient conditions or heat losses. These results verify the technical feasibility of flexible PCC operation and provide a suitable dataset for dynamic model validation.