Cucurbit[n]urils (CB[n]s, n = 5–8, 10, 13–15) have been proven to be an interesting macrocyclic family with their distinctive molecular recognition properties and fascinating applications in fields such as catalysis, supramolecular materials, drug delivery and biological systems. With the biggest cavity in the CB[n]s family, CB[10] shows its unique molecular recognition properties that are rather distinctive from other CB[n]s. In this review, we summarize the progresses in CB[10]-based chemistry since CB[10] was first reported as CB[10]·CB[5] complex in 2001. Purification, molecular recognition and supramolecular assembly of CB[10] will be described and an outlook will be given for further exploration of CB[10]-based chemistry.