Taking advantage of a rigid tetradentate ligand of bis(pyrazoly)(3-pyrazolypyridinyl)methane (PyPz(3)) and the [Cu-II(opba)](2-) unit [opba(4-) = o-phenylenebis(oxamato)], the trinuclear complex [{Co-II(PyPz(3))}(2)Cu-II(opba)][ClO4] 2 center dot 5MeCN center dot MeOH (1) was constructed, in which the Co-II centers adopt a trigonal-prismatic geometry, while considerable intramolecular magnetic coupling was successfully introduced through the oxamido bridges, representing another very first example of single-molecule magnets marrying both selected coordination geometry and magnetic exchanges.