The hexacopper(II) siloxanolate cage Cu6{(PhSiO2)6}2(BuOH)5*3 nBuOH has been synthesized by reaction between CuCl2 and potassium phenylsiloxanolate in n-butanol, and characterized by single-crystal X-ray diffraction, magnetic measurements and high-frequency EPR (HF-EPR). The complex exhibits a torus-like structure featuring a layer of six copper(II) ions sandwiched between two cyclic (PhSiO2)66- ligands and surrounded by nBuOH molecules. The magnetic properties are characterized by moderate ferromagnetic exchange interactions between the S=1/2 copper(II) centres to give an S=3ground spin state. Variable temperature HF-EPR spectra evidence a hard-axis magnetic anisotropy with g||=2.063, g=2.225and D=0.31cm-1. The cage is very soluble in organic solvents and, upon exchange of the labile nBuOH ligands, it functions as a high-spin hexatopic receptor for monodentate units. Reaction with the trigonal bipyramidal copper(II) mononuclear Cu(tmpa)CN+ in CHCl3/MeOH solution (tmpa=tris(2-pyridylmethyl)amine) affords the decacopper(II) complex Cu6{(PhSiO2)6}2{NCCu(tmpa)}4(PF6)4, whose X-ray structure and magnetic behaviour are presented.