Metal-organic vesicular and toroid nanostructures of Zn(OPE)·2H2O are achieved by coordination-directed self-assembly of oligo-phenyleneethynylenedicarboxylic acid (OPEA) as a linker with Zn(OAc)2 by controlling the reaction parameters. Self-assembled nanostructures are characterized by powder X-ray diffraction, field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and adsorption study. The amphiphilic nature of the coordination-polymer with long alkyl chains renders different soft vesicular and toroidal nanostructures. The permanent porosity of the framework is established by gas adsorption study. Highly luminescent 3D porous framework is exploited for Froster's resonance energy transfer (FRET) by encapsulation of a suitable cationic dye (DSMP) which shows efficient funneling of excitation energy. These results demonstrate the dynamic and soft nature of the MOF, resulting in unprecedented vesicular and toroidal nanostructures with efficient light harvesting applications.