In this review the most important techniques developed to hyphenate CE to MALDI-TOF-MS are summarized. The principles of the different interfaces and ways to solve the hyphenation problem are explained and discussed in detail. The most important applications especially in the proteomic field are reviewed, and the advantages of CE-MALDI-TOF-MS for the analysis of these compounds compared to other techniques such as ESI-MS are exhaustingly discussed from a critical point of view. CE coupled to MALDI-TOF-MS has started to overpass traditionally used CE-coupling techniques, especially CE-ESI-MS, offering the possibility to analyze samples of interest even weeks after CE analysis and using multiplexing systems for high-sample throughput.