Density functional theory (DFT) has been used to assess the pi-acidity and pi-basicity of metal-organic trimetallic macromolecular complexes of the type [M(mu-L)]3, where M = Cu, Ag, or Au and L = carbeniate, imidazolate, pyridiniate, pyrazolate, or triazolate. The organic compounds benzene, triazole, imidazole, pyrazole, and pyridine were also modeled, and their substituent effects were compared to those of the coinage metal trimers. Our results, based on molecular electrostatic potential surfaces and positive charge attraction energy curves, indicate that the metal-organic macromolecules show superior pi-acidity and -basicity compared to their organic counterparts. Moreover, the metal-organic cyclic trimers are found to exhibit pi-acidity and -basicity that can be systematically tuned both coarsely and finely by judicious variation of the bridging ligand (relative pi-basicity imidazolate > pyridiniate > carbeniate > pyrazolate > triazolate), metal (relative pi-basicity Au > Cu > Ag), and ligand substituents. These computational findings are thus guiding experimental efforts to rationally design novel [M(mu-L)]3 materials for applications in molecular electronic devices that include metal-organic field-effect transistors and light-emitting diodes.