Peryleneimide compounds are industrially important pigments in paint industries as well as in electronics areas. We have focused on the title compound (BIP) as a potential substitute for carbon black used widely as the black pigment. For this reason, electronic characterization of the cis and trans form of BIP has been carried out on the basis of the crystal structure and intermolecular interactions. The black color is characterized by two absorption bands in the visible region in both isomers: the former, shorterwavelength band is due to individual molecules and the latter, longer-wavelength band appears as a result of excitonic interactions between transition dipoles. The stack molecule-pairs, among others, play the determinant role in the appearance of the longer-wavelength band to cover the whole visible region together with the molecular band.