Self-assembly of the perylene segment leads to vesicle formation of perylene end-capped poly(dimethylsiloxane) (PDMS) in nonaqueous media. The perylene self-assembles into crystalline aggregate, with a well-defined melting temperature and reversible melting and crystallization. The T-m of the perylene aggregates increases with an increase in the length of the PDMS chain. The absorption spectra depend on the solvent used. TEM images show that a trilayer vesicle structure is formed with hexane mixtures. Thus, the packing of perylene depends on the choice of the solvent system. This initial attempt to prepare such vesicles in nonaqueous media may be applicable to similar systems.