Ten meso-tetraphenylporphyrin-type heterodimers containing a partly or completely β-brominated subunit were synthesized and characterized by UV-visible spectroscopy, cyclic voltammetry and spectroelectrochemistry, showing the presence of low electronic interactions between the two subunits. The investigated compounds are represented as M [( tripp - tpp ( Br 4)] M and M [ tripp - tpp ( Br 8)] M ( M = 2 H , Zn , Ni , Co and Cu ) where tripp - tpp ( Br 4) is the tetraanion of 1-[5-(10,15,20-triphenylporphyrinyl)]-4-[10-(2,3,12,13-tetrabromoporphyrinyl)]-benzene and tripp - tpp ( Br 8) is the tetraanion of 1-[5-(10,15,20-triphenylporphyrinyl)]-4-[10-(2,3,7,8,12,13,17,18-octabromoporphyrinyl)]-benzene. One of the synthesized dimers, H 2[ tripp - tpp ( Br 8)] H 2, was characterized by a single-crystal X-ray investigation.