Harvesting solar energy into chemical energy is a major challenge for scientists. So far conjugated polymer solar cells device placed a bench mark in organic solar cell research domain. But their photovoltaic performances stops after 5% efficiency due to inhomogeneous nanoscale morphology of donors and acceptors. Thus, supramolecular chemist wants to improve their photovoltaic performance by constructing an ordered, oriented and high hierarchical architecture on solid surface. Matile and co-workers introduced a high hierarchical network, called zipper assembly. Dream zipper assembly will be “panchromatic zipper assembly” which can absorb solar illumination AM 1.5. But it is still not clear whether blue NN-NDI chromophore can integrate into zipper assembly or not. To tackle this problem, we have synthesized NN-NDI-OPE hybrids. These molecules are subjected to zipper assembly formation. But it generates little photocurrent due-to energy mismatch between n-transporting NDI and p-transporting OPE. Whereas FF value showed a high hierarchical network formed in NN-NDI-OPE zipper assembly. Thus to achieve an optoelectronically matched zipper assembly we have finely tuned p-transporting channel. Oligothiophene (OT) is considered first as our next optoelectronic finely tuned p-transporter. OTs are widely used in polymer solar cell. There is no literature available where chromophores are installed in advance to construct solar cell. Thus we have synthesized NN-NDI-OT hybrids.