Two flexible ether bonds were designed to connect two pyrene rings on a polyhedral oligomeric silsesquioxane (BPy-POSS) to enrich the fraction of "intrinsic intramolecular pyrene-dimer" on the surface of crystal isobutyl-POSS (iBu-POSS) thin-films. Compared to the monomer emission of 1-pyrenemethanol (Py-OH), the emission spectra of BPy-POSS in dichloromethane show the large proportion of intramolecular and intermolecular excimers due to the formation of pyrenyl dimers or aggregates via the easy rotation of two adjacent ether bonds and the pi-pi interaction of pyrene rings, respectively. By blending inert iBu-POSS, the fluorescent dimers or aggregates of 5 wt.% and 20 wt.% BPy-POSS are distributed on the surface of iBu-POSS crystal fractal pattern as shown by confocal photoluminescence microscopy. Upon exposure to the vapors of nitrobenzene, the 5 wt.% BPy-POSS blend shows the similar quenching efficiency as 100 wt.% BPy-POSS blends, indicating the better excimer dispersion for vapor permeability of blend thin-films. (c) 2011 Elsevier Inc. All rights reserved.