Wedge- and dumbbell-shaped amphiphilic perylene bisimides PBI 1-4 were synthesized. The wedge-shaped PBI 1 and PBI 2 and dumbbell-shaped PBI 4 self-assemble into micelles, and rod aggregates in aqueous solution, respectively. Interestingly, the co-self-assembly of wedge-shaped PBI 1 with dumbbell-shaped PBI 3 generates hollow vesicles with bilayer structures because of the curvature changes during the self-assembly process. The bilayer vesicles could be stabilized by in situ photopolymerization.