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It is difficult for the same molecule to form vesicular assemblies in water and alipatic hydrocarbon (oil), respectively. Here, we report that chiral oligmethylene-p-phenyleneethynylene)s bearing hydrophobic or hydrophilic side chains can take extended conformations to self-assemble into vesicle-like particles in a hydrophobic or hydrophilic solvent system. The self-assembly processes are highly independent of molecular design and chemical environments. Based on the analyses of TEM, UV, CD and PXRD data, it is plausible to expect tha