In the present study, a etoxymethylresorcinarene (EMR) is used as a trap for C60 molecules at the air−water interface. The resulting self-assembled EMR:C60 complexes form stable well-ordered monolayers which can be easily transferred to a solid substrate. The interlayer charge transfer between poly(3-hexylthiophene) (PHT) and C60 was studied using the time-resolved Maxwell displacement charge (TRMDC) method. The structural details of the EMR molecule were calculated by means of molecular mechanics, semiempirical and ab initio methods. The computational results predict that there is enough space for the C60 molecule to be placed between the tails of the resorcinarene molecule.