We describe a photochemical method to introduce a single alcohol function directly on cucurbit[n]urils (n = 5, 6, 7, 8) with conversions of the order 95-100% using hydrogen peroxide and UV light. The reaction was easily scaled up to 1 g for CB and CB. Spin trapping of cucurbituril radicals combined with MS experiments allowed us to get insights about the reaction mechanism and characterize CB, CB, CB, and CB monofunctional compounds. Experiments involving 18O isotopically labeled water indicated that the mechanism was complex and showed signs of both radical and ionic intermediates. DFT calculations allowed estimating the Bond Dissociation Energies (BDEs) of each hydrogen atom type in the CB series, providing an explanation of the higher reactivity of the "equatorial" C-H position of CB[n] compounds. These results also showed that, for CB, direct functionalization on the cucurbituril skeleton is more difficult because one of the methylene hydrogen atoms (H<inf>b</inf>) has its BDE lowering within the series and coming close to that of H<inf>c</inf>, thus opening the way to other types of free radicals generated on the CB skeleton leading to several side products. Yet CB-(OH)<inf>1</inf> and CB-(OH)<inf>1</inf>, the first CB derivative, were obtained in excellent yields thanks to the soft method presented here.