This review summarizes the principle and the developments in MEKC in terms of separation power, sensitivity, and detection approaches more than 25 years after its appearance. Newly used surfactants are mentioned. Classical and new sample concentration techniques in MEKC are described. The different detection approaches in MEKC with advantages, limitations, and future prospects are also discussed. This review highlights the wider application of MEKC in different analytical fields. Various recent selected applications of this technique in different analytical fields are reported.