This review deals with the current status of important separation techniques using capillary NMR detection. The advantages and disadvantages of the different hyphenated methods are discussed referring to a specific application. The use of Capillary-HPLC-NMR is demonstrated on an identification method of two bixin stereoisomers. The huge advantages using an HPLC-SPE-NMR method for structure determination are explained and discussed. Furthermore, two uncommon coupling techniques such as CE-NMR and GC-NMR are described in this review article.