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Donor–acceptor dyads are very promising compounds for low-cost organic photovoltaic devices. The orientation of porphyrin–fullerene dyads TBD6a and DHD6ee formed on a solid substrate by the Langmuir–Schaefer method is considered. It was shown by X-ray reflectivity that molecular orientation persisted during that transmission from liquid to solid surface in spite of the dyad molecules low anisometry.