Characteristic luminescence from the assembled species of [Pt(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 thei-biq complex, a broad emission band (λmax= 680 nm) appears with increasing concentration in addition to a3ππ*emission band form the monomer complex (λmax= 528 nm). The broad band is attributable to the emission from the3MLCT 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 sharp3ππ*emission. However, the broad emission has an excimeric character. The π-π interaction between the π-conjugated ligands would be an important factor in the assemblage of the platinum complexes in the dilute system.