The use of the binary "blend" of MeCO(2)(-)/pdmH(2) ligands (pdmH(2) = pyridine-2,6-dimethanol) in copper(II) chemistry has provided access to a compound consisting of discrete linear Cu(II)(3) and cubane Cu(II)(4) clusters. The complicated magnetic behavior of the Cu(II)(3) + Cu(II)(4) complex was clarified and interpreted through the designed synthesis of the individual Cu(II)(4) component; a unique 1D (Cu(II)(5))(n) compound containing a Cu(II)(3) subunit, which is structurally similar to the trinuclear cluster in the Cu(II)(3) + Cu(II)(4) compound, was also isolated and structurally characterized.