A series of novel CdII complexes based on α,β-unsubstituted dipyrrin ligands (dpm) has been prepared and characterised both in solution and in the solid state. These compounds are of the [Cd(dpm)2] type, with the coordination sphere of the metal centre occupied by two dpm chelates. Interestingly, in contrast to what has been reported for the ZnII analogues, in the presence of a pyridyl- or imidazolyl-appended dpm ligand, the coordination number of the CdII cation can be increased to six, leading to an octahedral coordination sphere. As a consequence, the formation of 1-, 2-, and 3D coordination polymers by self-assembly is observed. Photophysical investigations of the discrete complexes and self-assembled networks have demonstrated that both types of compounds are luminescent in the solid state.