As the development of chemical absorption technology for post-combustion capture (PCC) of CO2 from coal-fired power station flue gases proceeds towards commercial deployment, the focus on establishing a thorough understanding of the degradation of the aqueous amine absorbents is increasing. However, there is a need to develop and demonstrate robust analytical methods that are capable of measuring the concentrations of amine degradation products in aqueous monoethanolamine (MEA) matrix during pilot-scale PCC. In this study, sample cleanup and derivatisation methods that enable reliable and robust analysis of MEA degradation products by GC–MS are described. Two sample cleanup methods were evaluated: dehydration (by rotary evaporation and molecular sieves) and cation exchange. The cation exchange sample preparation method was preferred for the analysis of organic degradation products in these samples because it achieved higher recovery and repeatability of GC–MS measurements than those obtained with the dehydration method. Furthermore, the cation exchange method resulted in less continued amine degradation during subsequent analysis steps because of its ability to separate acidic analytes from basic analytes, as well as to remove some inorganic interferences. Further improvement of the sensitivity, repeatability and accuracy of this GC–MS analytical method can be accomplished by: (a) increasing the scale of the cation exchange and/or derivatisation procedures; (b) optimizing the derivatisation reaction conditions; and (c) using a narrower bore (e.g. 0.25 mm ID) GC–MS column. The proposed cation exchange and derivatisation procedures can be readily adopted for the quantification of organic degradation products in other aqueous amine absorbents to provide important insights into the degradation of amine absorbents during PCC of CO2.