Perylene Tetracarboxylic Diimides (PDI) have found a wide variety of applications in optoelectronic devices including solar cells, LCD's, LED's, FET's and chemosensors due to its stability, high fluorescence and good n-type semiconductors. It will create a special constrained π - π interaction if nanoparticle with good solubility, unique electronic properties and bigger size than 0.4 nm is tethered to PDI. The resulted molecular-level nanohybrids are possible to be new kinds of optoelectrinic materials. A facile one pot procedure has been developed to synthesize series of asymmetric PDIs tethered by POSS and/or C60. The components have been well characterized by NMR, MALDI-TOF mass spectrometry, TGA and DSC. The self-assembly behavior depends on molecular structure and selective mixture solvent system. The POSS-PDI-OH with flexible propyl connection can be self-assembly to fluorescent belt-like crystal due to rotated or discontinued p-p stacking. POSS-PDI-C60 with flexible propyl connection has potentially use in photovoltaic.