Characteristic luminescence from the assembled species of [Pr(CN)(2)(L)] (L = 3,3'-biisoquinoline (i-biq) and 2,2'-bipyridine (bpy)) has been found in a dilute EtOH-MeOH (4:1 v/v) glassy solution at 77 K. For the i-biq complex, a broad emission band (lambda(max) = 680 nm) appears with increasing concentration in addition to a (3)pi pi* emission band form the monomer complex (lambda(max) = 528 nm). The broad band is attributable to the emission from the (MLCT)-M-3 state of the assembled species with the Pt-Pt intermolecular interaction. In the case of the bpy complex, similar broad emission is also observed as well as the sharp (3)pi pi* emission. However, the broad emission has an excimeric character. The pi-pi interaction between the pi-conjugated ligands would be an important factor in the assemblage of the platinum complexes in the dilute system.