Steady-state and time-resolved fluorescence techniques were used to study the thermodynamics of binding of a neutral polarity-sensitive guest, the methyl 2-naphthalenecarboxylate (2MN), with three cucurbiturils (CBn; n=6, 7 and 8) in water. Association constants (K) were obtained from nonlinear regression analysis of the fluorescence intensity against [CB] in the 5-45 degrees C range. 2MN complexed with CB7 exhibited a 1:1 stoichiometry (K approximate to 10(3)M(-1) at 25 degrees C); however, it hardly did with CB6 (K<10M(-1)) and it did not with the larger CB8 macrocyclic ring. The (1:1) 2MN:CB7 complexation process was accompanied by a small unfavourable enthalpy change and was, therefore, entropically governed. Molecular mechanics and molecular dynamics calculations in the presence of water were also used to study the geometry of the complexes formed and the driving forces responsible for their formation. The results were compared with those previously obtained for the complexation of the same guest, 2MN, with natural -, - and -cyclodextrins.