Cucurbit[n]uril(Q[n])-based supramolecular frameworks assembled through outer surface interactions are characterized by their simple composition, convenient preparation, high yields and controllable structures. The most prominent characteristic of these frameworks is their diversity, with various synthesis methods, structural characteristics, structure directing agents and basic building blocks of Q[n]s. In this work, a symmetric tetramethyl-substituted Q[6] (TMeQ[6]) is selected as the basic building block, with three different TMeQ[6]-based supramolecular frameworks obtained from 1-, 3- and 5 mol/L aqueous H2SO4 solutions, respectively. The outer surface interactions between TMeQ[6] and the adjacent SO42- anions or TMeQ[6] units are the main driving forces for the formation of these frameworks, which exhibit adsorption properties for fluorophore dyes and organic isomers. These adsorption characteristics may lead to the application of these frameworks in the synthesis of solid fluorescent sensors for volatile organic compounds and the adsorptive separation of alkane isomers. [GRAPHICS] .