A new complex of trinuclear silver(I) pyrazolate macrocycle [AgPz]3 (Pz = (CF3)2Pz) with 4,4′-dibromobiphenyl (L) was synthesized and characterized. As shown by NMR spectroscopy, X-ray diffraction (CCDC no. 2169289), and quantum chemical calculations, the π-electron density of the aromatic ligand serves as the coordination site both in solution and in the solid state. The bromine atom is not coordinated to the metal. The complexation gives rise to infinite columns composed of alternating macrocycle and biphenyl molecules {[AgPz]3·L}∞. The neighboring columns are linked by shortened Br–FCF3 contacts. In the solid state, the biphenyl geometry is flattened (the dihedral angles are 0.68° and 0.51°), which has the crucial effect on the photophysical behavior of the complex and demonstrates the possibility of controlling photoluminescence properties of oligophenylene systems. [ABSTRACT FROM AUTHOR]