This updated review is focused on the applications of CE in phytochemical analysis during the period of 2014 to April 2018 (about 130 papers were included). The article mainly consists of three main sections, including sample pretreatment (extraction and on‐line pre‐concentration), method development (separation and detection) and applications in quality evaluation of medicinal plants, screening of active compounds (enzyme inhibitors) and studying interaction between phytochemicals and bio‐macromolecules.