Cyclic voltammetric and UV/vis and EPR spectroelectrochemical studies of new synthesized series of pyrrolylbenzenes indicate different oxidation products depending on the number of pyrrole units on the phenyl ring and on the pyrrole substitution. Both intra- and intermolecular coupling of charged monosubstituted hexapyrrolylbenzenes is evidenced from cyclovoltammetric and spectroelectrochemical studies. The optical and electrochemical properties as well as the extent of the intermolecular coupling strongly depend on the alpha and beta substitution of I-N-pyrrolyl group. (c) 2007 Elsevier Ltd. All rights reserved.