The solid state structures of the copper(II) Schiff base complexes [{Cu(1)}(H₂O)], [Cu(1)(OH₂)]·MeCN and [({Cu(1)}(H₂O))₂(2)] (H₂1 = N,N′-(1R,2R)-(–)-1,2-cyclohexylenebis(3-ethoxysalicylideneamine) and 2 = naphthalene-2,6-dicarboxylic acid) exhibit two recurring structural motifs: host–guest, hydrogen-bonded recognition of H₂O in the O,O′,O″,O‴-cavity of [Cu(1)], and face-to-face stacking of [Cu(1)] units with non-bonded Cu⋯Cu separations of 3.54–4.89 Å. In [{Cu(1)}(H₂O)], the H₂O molecule is non-coordinated to the copper(II) centre whereas in [Cu(1)(OH₂)]·MeCN it is axially bound to the copper(II) atom while retaining its role as a hydrogen-bonded guest in the O,O′,O″,O‴-cavity of an adjacent [Cu(1)] molecule. The guest H₂O molecule in [{Cu(1)}(H₂O)] can function as a hydrogen bond donor as illustrated by the assembly of [({Cu(1)}(H₂O))₂(2)]. Solution (in THF) electronic spectroscopic data for the complexes are consistent with dissociation of the building blocks including the cleavage of the Cu–OH₂ coordination bond. The self-assembly and structural diversity are discussed in terms of a series of hierarchical events.