The aggregation-induced emission enhancement (AIEE) characteristics of the two alkoxy-bridged binuclear Re(I) complexes [{Re(CO)3(1,4-NVP)}2(mu(2)-OR)(2)] (1, R = C4H9; 2, C10H21) bearing a long alkyl chain with 4-(1-naphthylvinyl)pyridine (1,4-NVP) ligand are illustrated. These complexes in CH(2)C1(2) (good solvent) are weakly luminescent, but their intensity increased enormously by almost 500 times by the addition of poor solvent (CH3CN) due to aggregation. By tracking this process via UV-vis absorption and emission spectral and TEM techniques, the enhanced emission is attributed to the formation of nanoaggregates. The nanoaggregate of complex 2 is used as a sensor for nitroaromatic compounds. Furthermore, the study of the photophysical properties of these binuclear Re(I) complexes in cationic, cetyltrimethylammonium bromide (CTAB), anionic, sodium dodecyl sulfate (SDS), and nonionic, p-tert-octylphenoxypolyoxyethanol (TritonX-100, TX-100), micelles as well as in CTAB-hexane-water and AOT-isooctane-water reverse micelles using steady-state and time-resolved spectroscopy and TEM analysis reveals that the nanoaggregates became small and compact size.