A comparative study on oligo(p-phenylene vinylene) (OPV)-appended porphyrins containing all trans-vinylene (either hydrophilic or lipophilic) or amide linkages (lipophilic) is presented. The type of supramolecular arrangement obtained in organic solvents proves to be strongly dependent on the nature of the covalent connection. In the case of all trans-vinylene linkages, a J-type intermolecular packing is obtained and the assemblies are only of moderate stability. Conversely, the supramolecular structures obtained from the amide-linked system display an H-type stacking arrangement of enhanced stability and chirality as a consequence of intermolecular hydrogen bonding along the stack direction, favorably interlocking the stacked building blocks. Interestingly, the observed differences in stability and organization are qualitatively illustrated by monitoring the sequential energy transfer process in both types of assemblies. Efficient intramolecular energy transfer from the OPVs (donors) to the respective porphyrin cores is followed by energy transfer from Zn-porphyrin (donor) to free-base porphyrin (acceptor) in both systems. However, the improved intermolecular organization for the amide-linked system increases the energy transfer efficiency along the stack direction. In addition, the water-soluble (OPV)-appended porphyrin system forms highly stable assemblies in an aqueous environment. Nevertheless, the poor energy transfer efficiency along the stack direction reveals a relative lack of organization in these assemblies.