Three cage-like polycyclic compounds, viz. exo-8-(trifluoromethyl)pentacyclo[5.4.0.0(2,6).0(3,10).0(5,9)]undecan-endo-8-ol, C12H13F3O, 5-(trifluoromethyl)-4-oxahexacyclo[5.4.1.0(2,6).0(3,10).0(5,9).0(8,11)]dodecan-3-ol, C12H11F3O2, and N-[exo-11-(trifluoromethyl)-endo-11-(trimethylsilyloxy)pentacyclo[5.4.0.0(2,6).0(3,10).0(5,9)]undecan-8-ylidene]aniline methanol solvate, C21H24F3NOSi.CH4O, were obtained from the corresponding oxo derivatives by nucleophilic trifluoromethylation with (trifluoromethyl)trimethylsilane in 1,2-dimethoxyethane solution in the presence of CsF. The crystal structures show that the addition of trifluoromethanide occurs exclusively from the exo face of the polycyclic ketones. Further examination of the crystal structures, together with that of the starting pentacyclo[5.4.0.0(2,6).0(3,10).0(5,9)]undecane-8,11-dione, C11H10O2, showed that increasing substitution at the 8- and/or 11-positions in the cage molecules increases the non-bonded intramolecular C...C distances at the mouth of the cage and changes the puckering of the five-membered rings involving the 8- and 11-positions from an envelope towards a distorted half-chair conformation. Intermolecular co-operative O-H...O hydrogen bonds in the endo-8-ol compound link the molecules into tetramers.