Amine-based post-combustion CO2 capture (PCCC) technology is regarded as one of the most viable solutions for the mitigation of CO2 emissions. It has been mature enough to be implemented on commercial scales. However, N-nitrosamines and N-nitramines can be formed as by-products of amine degradation during PCCC processes. They are suspected carcinogens and strictly regulated. With the development of PCCC technology across the global, PCCC facility may become a main source of N-nitrosamines and N-nitramines to the environment. Due to the possible adverse effects of N-nitrosamines and N-nitramines on the environment and human health, the interests in the occurrence, fate and mitigation of PCCC-derived N-nitrosamines and N-nitramines have been shared by a growing number of researchers recently. Therefore, this article provides a comprehensive review on the most recent efforts in this emerging field. In detail, this review focuses on (a) the formation, emission and degradation of N-nitrosamines and N-nitramines from amine-based PCCC processes, (b) the toxicology and environmental impact of PCCC-derived N-nitrosamines and N-nitramines, (c) the methods to destruct and remove N-nitrosamines and N-nitramines from PCCC waste, and (d) the future research perspectives.