Reactions of (NH4)2[MoOS3] with [Cu(MeCN)4](ClO4) and bis(3,5-dimethylpyrazolyl)methane (dmpzm) (molar ratio = 1:3:3) in MeCN produced a cationic cluster [MoOS3Cu3(dmpzm)3](ClO4) (1). 1 consists of a unique 3D hydrogen-bonded network with empty C3-symmetry cavities. A set of C3 (cyclohexane) or non-C3-symmetry solvent molecules (aniline, N,N′-dimethylformamide, formamide, and water) could recognize these C3-symmetry cavities and smartly fit themselves into them by converting themselves into C3-symmetry species through intriguing ways of symmetry-oriented molecular disorder and trimerlization.