The title complex, {(N,N'-dimethyl-4,4'-bipyridinium)[Cd 2 (ȝ 2 -Cl) 4 Cl 2 ]} n (1), in which the N,N'-dimethyl-4,4'-bipyridinium was generated in situ, was synthesized via hydrothermal reaction. X-Ray diffraction analysis revealed that the structure of 1 consisted of MV 2+ (MV 2+ = N,N'-dimethyl-4,4'-bipyridinium) cationic moieties and infinite [Cd 2 (ȝ 2 -Cl) 4 Cl 2 ] n anionic chains. The cadmium atom was bound by one terminal chlorine atom and four ȝ 2 -bridging chlorine atoms, yielding a slightly distorted triangular bipyramid. Photoluminescent investigation revealed that the complex displayed an emission in greenish blue region.