New C-60-TTF dyads with several substituents on the TTF moiety were prepared to examine the substituent effect on the intramolecular charge transfer interaction. Cast films of the dyads with long alkyl chains were obtained with high quality and characterized. In X-ray diffraction study for the cast film of the derivative with -SC16H33 groups (1g), high ordered reflection peaks were observed. Analysis of the diffraction pattern revealed that 1g forms the multibilayer structure in condensed film.