The C60‐pyridine, C60py, and C60‐imidazole, C60im, adducts were found to self‐assemble in films floating onto aqueous solutions of zinc tetrakis (N‐methylpyridinium)porphyrin cation, Zn(TMPyP), or zinc tetrakis (4‐sulfonatophenyl)porphyrin anion, Zn(TPPS). This self assembling was due to axial ligation of the C60adducts (acceptors) by Zn porphyrins (donors), which lead to the formation of relatively stable donor‐acceptor dyads in the water‐air interfaces. The films were compressed in a Langmuir trough and characterized by isotherms of surface pressure vs. area per molecule as well as by the Brewster angle microscopy imaging. All systems formed stable aggregated Langmuir films of the “expanded liquid” type. Extensive compression of the films resulted in two‐dimensional phase transitions. The area per molecule at infinite dilution of the adducts in films increased in the order: water<0.1 mM Zn(TPPS)<0.1 mM Zn(TPMyP). Comparison of the determined and calculated values of area per molecule indicated that orientation of porphyrins in the complexes was parallel with respect to the interface plane. The Langmuir films were transferred, by using the Langmuir‐Blodgett technique, onto quartz slides. The UV‐vis spectroscopic study of these films revealed that Zn porphyrins were transferred together with the C60adducts and that the transfer efficiency increased in the order: C60py‐Zn(TPPS)<C60py‐Zn(TMPyP)<C60im‐Zn(TPPS)<C60im‐Zn(TMPyP), i.e., in accord with the increase of stability of the respective dyads in solutions. © 2003 American Institute of Physics