The combination of post-column derivatization (PCD) and liquid chromatography (LC) has become a promising technique for enhancing detection sensitivity and selectivity, while simultaneously facilitating rapid and automated analysis. This paper presents a comprehensive review of PCD techniques spanning from 2013 to 2023, focusing on LC-UV-Vis/fluorescence spectrometry and LC-mass spectrometry detection methods. It encompasses an array of PCD methods, including chemical, photochemical, and electrochemical derivatization, as well as post-column complexation. This review delves deeply into key areas, exploring the underlying principles of derivatization, examining the current applications of classical PCD methods, and shedding light on emerging derivatization reactions. The review also provides remarks and insights into future directions, offering a perspective on the evolving landscape of the field. The overarching goal is to equip researchers with innovative ideas and strategies for PCD, thereby enhancing the practical application and utility of this technology in scientific research. Display omitted •LC coupled PCD enhances detection sensitivity/selectivity.•Chemical/photochemical/electrochemical reactions and complexation are the main methods.•Advances in post-column derivatization techniques from 2013 to 2023 are reviewed.•Principles of derivatization reaction and their applications are examined.•Insights on future trends advancing post-column derivatization research are offered.