Donor-acceptor nanohybrids by a covalent linkage between the beta-position of a Zn(II)Porphyrin and multi-walled carbon nanotubes are reported for the first time, in a closer analogy to the natural light harvesting systems, which are based on beta-substituted porphyrinoid structures, the chlorophylls. An unique and direct connection was established through the immobilization of the Zn(II)(beta-NH2-tetra-phenylporphyrin), using diazonium chemistry, in order to afford i) a short and conjugated linkage between the two aromatic systems and ii) an amide bond resulting from a three-step functionalization synthesis. Electronic and steady-state fluorescence spectroscopies confirmed high photoinduced electron communication through the beta-linkage when compared to analogous meso-phenyl linkers, stating its positive effect. The procedure involving the amide linkage allowed higher chromophore loadings; however, the direct conjugated bond showed improved photoinduced activity and a different emission pattern that can be associated with intense communication within the expanded pi-system MWCNT-metalloporphyrin. (C) 2013 Elsevier B.V. All rights reserved.