Cucurbit [n] urils (CB [n]), a kind of host molecules of the fourth generation supramolecule followed crown ethers, cyclodextrins and calixarenes in supramolecular chemistry, are macrocyclic ligands and consist of several glycoluril units. Their special molecular recognition based on unique separation selectivity and stability have gained great interest in supramolecular chemistry and chromatography. Hereby, we give a review of research progresses of cucurbit [n] urils structural features, its homologues and derivatives and their applications in chromatographic stationary phase.